Systems and methods for processing gases

ABSTRACT

The invention includes a gas processing system for transforming a hydrocarbon-containing inflow gas into outflow gas products, where the system includes a gas delivery subsystem, a plasma reaction chamber, and a microwave subsystem, with the gas delivery subsystem in fluid communication with the plasma reaction chamber, so that the gas delivery subsystem directs the hydrocarbon-containing inflow gas into the plasma reaction chamber, and the microwave subsystem directs microwave energy into the plasma reaction chamber to energize the hydrocarbon-containing inflow gas, thereby forming a plasma in the plasma reaction chamber, which plasma effects the transformation of a hydrocarbon in the hydrocarbon-containing inflow gas into the outflow gas products, which comprise acetylene and hydrogen. The invention also includes methods for the use of the gas processing system.

RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.16/548,378, filed on Aug. 22, 2019, which claims the benefit of U.S.Provisional Application No. 62/721,863 filed on Aug. 23, 2018, U.S.Provisional Application No. 62/736,206 filed on Sep. 25, 2018, and U.S.Provisional Application No. 62/793,763 filed on Jan. 17, 2019. Theentire teachings of each of the above applications are incorporatedherein by reference.

BACKGROUND

Acetylene can be used as a chemical precursor or as a feedstock forindustrial combustion uses, such as welding and metal cutting.Commercial production of acetylene has been carried out since the earlytwentieth century. The original method for acetylene production utilizedcoal as the source material, through a process involving a calciumcarbide intermediary. Other methods were developed later in thetwentieth century, mainly using heat-based processes such as thermalcracking or electric arc furnaces.

Acetylene produced from coal involves a three-step process: first, coalis heated to produce high-carbon-content coke; second, the coke isheated further in the presence of calcium oxide to yield calciumcarbide; third, calcium carbide reacts with water to yield acetylene andcalcium hydroxide. The first two steps require very high temperatures,while the last step is exothermic. This method for forming acetylene isstill used commercially, especially in China where coal is readilyavailable.

This process, however, carries the impurities of the coal and limesource materials into the final product, so that the resulting acetyleneis contaminated with impurities such as phosphines, arsines, andhydrogen sulfate. All of these species are capable of poisoningcatalysts for subsequent chemical reactions, so that they need to bescrubbed from the acetylene product before it can be used commercially.Chemical grade acetylene, used for further chemical processing, mustbe >99.6% pure C₂H₂, with <25 ppm phosphine/arsine/H₂S.

Industrial grade acetylene, which is burned for welding and metalcutting applications, can tolerate more impurities (>98.0 pure C₂H₂,<500 ppm phosphine/arsine/H₂S). Therefore, the coal-derived productionof acetylene is limited in the U.S. to forming industrial gradeacetylene; still, even when coal-derived acetylene is just used forwelding and metal cutting, the presence of potentially hazardouscontaminants raises concerns.

As an alternative, acetylene can be prepared from hydrocarbons bypartial oxidation, for example by the process developed by BASF, asdescribed in U.S. Pat. No. 5,824,834. In this process, a hydrocarbonfeedstock and oxygen are preheated and then reacted in a combustionchamber, causing the produced gases to reach temperatures >1500° C. Thecombustion reaction is quenched with water to effect rapid cooling,yielding a gaseous mixture (called “cleavage gas”) of acetylene,hydrogen, carbon monoxide, steam and byproducts. This method ofacetylene production yields about 7.5% acetylene, along with largequantities of hydrogen (57%), carbon monoxide (26%), and methane (5.2%).One of the byproducts is soot, which needs to be removed from thecleavage gas as it is processed further. Other byproducts includehigher-order hydrocarbons, including alkanes, alkenes, alkynes, andaromatics. Removing the impurities from the cleavage gas and recoveringthe acetylene it contains involve significant engineering challenges.

In addition to the production issues, acetylene is difficult to handleand transport. It is highly explosive. When transported throughpipelines, it is kept at a low pressure and is only conveyed for shortdistances. Acetylene for industrial purposes is pumped into tanks athigh pressure and dissolved in solvents, for example, dimethylformamide,N-methyl-2-pyrrolidone, or acetone. When the acetylene cylinder isopened, the dissolved gas vaporizes and flows through a connecting hoseto the welding or cutting torch. The entire amount of acetylene in acylinder is not usable however, because a certain amount remainsdissolved in the solvent and is returned to the manufacturer in thisstate. With the rise of the petrochemical industry in the mid-twentiethcentury, acetylene continued to be used industrially (i.e., for welding,metal cutting and the like) but it was displaced as a precursor forchemical reactions, replaced by other feedstocks (e.g., ethylene) thatwere derived directly from oil rather than from coal. As oil has becomemore expensive and natural gas has become cheaper though, there isincreased interest in acetylene as a platform for further chemicalprocessing instead of petroleum-derived feedstocks.

Moreover, the abundance of natural gas is driving the search for moreways to use this material without burning it, to decrease its greenhousegas effects and to avoid transforming it into CO₂, another greenhousegas, by simple combustion. Increasing demand for non-hydrocarbon sourcesof fuel supports the use of natural gas as a feedstock for producinghydrogen, which in turn can be used as a source of power. Conventionaltechnologies already exist for extracting hydrogen gas from the methanein natural gas. Steam reforming, for example, can produce hydrogen gasand carbon monoxide; the hydrogen created by the steam reforming processcan then be used in pure form for other applications, such as hydrogenfuel cells or gas turbines, in which it combines with oxygen to formwater, without greenhouse gas emissions. Other processes, such aspartial oxidation, can produce a hydrogen-containing syngas, acombustible mixture that can be used as a fuel. Conventional techniquesfor producing hydrogen from methane have drawbacks, however. Steamreforming is carried out at high temperatures, and is energy-intensive,requiring costly materials that can withstand the harsh reactionconditions. Steam reforming uses catalysts to effect the conversion ofmethane to hydrogen, but the catalysts are vulnerable to poisoning bycommon contaminants. Partial oxidation is a less efficient techniquethan steam reforming for producing hydrogen, being prone to sootformation, and being limited in hydrogen yield.

Besides natural gas, other mixed gas sources such as oceanic clathrates,coal mine gas, and biogas contain methane gas as well. Biogas isnaturally produced mixed gas source that is produced by the anaerobicdecomposition of organic waste material in various human-createdenvironments such as landfills, manure holding ponds, waste facilities,and the like, and in natural environments such as peat bogs, meltingpermafrost, and the like. The anaerobic bacteria that occur in suchenvironments digest the organic material that accumulates there toproduce a gas mixture composed mainly of carbon dioxide and methane.Biogas with a high methane content, as can be found in landfill-derivedgas mixtures, can be hazardous, because methane is potentiallyflammable. Moreover, methane is a potent greenhouse gas. Currentlybiogas that is collected from organic decomposition (e.g., landfills,waste facilities, holding ponds, and the like, or natural regionscontaining decaying organic materials) can be purified to remove the CO2and other trace gases, resulting in a high concentration of methane forproducing energy. However, simply burning methane-rich biogas producesCO₂, another greenhouse gas. It would be desirable to identify uses forbiogas or other mixed gas sources that can exploit their energypotential without burning them, to decrease the greenhouse gas effectsof methane while avoiding transforming methane into another greenhousegas, CO₂.

There is a need in the art, therefore, for a process that utilizes mixedgas sources such as natural gas or biogas, and/or more purifiedhydrocarbon feedstocks (e.g., methane, ethane, propane, and butane, andcombinations thereof) to form higher-value products. For those processesintended to produce acetylene, it would be advantageous to use mixed gassources such as natural gas or biogas, and/or more purified hydrocarbonfeedstocks (e.g., methane, ethane, propane, and butane) as a feedstock,avoiding the limitations of other mixed gas conversion processes orhydrocarbon combustion processes while taking advantage of the abundanceof these feedstock materials. Concomitantly, there is a need in the artfor a process that can produce acetylene in a convenient andcost-effective way, using mixed gas sources such as natural gas orbiogas, and/or more purified hydrocarbon feedstocks. It would beespecially advantageous to produce acetylene with minimal impurities, sothat it can be used safely and without substantial additionalprocessing. Furthermore, there is further a need in the art to providealternative fuels such as hydrogen scalably and efficiently. It would bedesirable to carry out these processes in an economic andenvironmentally responsible way.

In addition, acetylene has utility as a fuel for various industrialapplications, for example, metal cutting. This use represents asignificant market, comparable in size to various petrochemical uses ofacetylene. At present, a major industrial use of acetylene is as a fuelfor oxyacetylene torches, used for cutting steel; in addition tocutting, acetylene is used in some welding, carburization, andheat-treating of steel. Oxyacetylene torches burn at a higher flametemperature (3,500° C.) than other oxy-fuel torches, such asoxy-hydrogen (3,000° C.) and oxy-propane (2,500° C.) torches, andoxyacetylene forms a smaller, more precise flame cone. These featuresallow for higher quality and more precise cutting than other comparableoxy-fuel cutting methods. Additionally, because the combustion ofacetylene requires a smaller stoichiometric ratio of oxygen than otherfuels like propane, the oxy-acetylene torches consume less oxygen thanother oxy-fuel torches, leading to lower oxygen operational costs.Finally, the lower flame temperature and higher oxygen requirements ofother hydrocarbon fuel types like oxy-propane torches allow for a higherrisk of incomplete combustion, producing hazardous carbon monoxide inthe work environment. For the aforesaid reasons, oxy-acetylene cuttingis standard in the industry for steel cutting.

However, as described previously, there are limitations in theproduction of acetylene and its transportation. Therefore, sourcingacetylene for industrial cutting is expensive and logisticallychallenging. First of all, acetylene used as a fuel for torches must betransported and stored in small metal cylinders because of the risk ofexplosion. In order to reduce the risk of explosion, the acetylene inthe cylinders is dissolved in acetone, lowering its partial pressure andthus the likelihood of explosion. Because acetone is present in thecylinders along with acetylene, the acetylene can only be drawn at lowflow rates (for example, not to exceed 1/7 of the container contents perhour), to reduce the chance of acetone being drawn into the outflow linealong with the acetylene—acetone in the gas feed can diminish flametemperatures and the quality of the cutting process. Even with low ratesof outflow, the acetylene in the cylinders can be depleted quickly; oncedepleted, a cylinder cannot be refilled on-site without extensive safetyinfrastructure and expertise, again because of the risk of explosion.Because of their small size, cylinders do not scale well for largeroperations, but instead must be connected in parallel via manifolding,adding to a project's complexity. Also, because of the risk ofexplosion, cylinders require a number of safety precautions as they aretransported, adding costs and logistical challenges.

There remains a need in the art for a more streamlined, safe method ofsourcing acetylene. It would be desirable to circumvent the need foracetone-containing cylinders as the repository for acetylene gas that isused in metal working. For example, it would be useful to have acetylenefuel available on demand and as needed, avoiding the volume and flowrate constraints of cylinder storage. In addition, it would also beadvantageous to have acetylene produced in proximity to the point of itsuse to avoid the cylinder-specific difficulties with transportation.

SUMMARY

Disclosed herein, in embodiments, are gas processing systems fortransforming a hydrocarbon-containing inflow gas into outflow gasproducts, comprising a gas delivery subsystem, a plasma reactionchamber, and a microwave subsystem, wherein the gas delivery subsystemis in fluid communication with the plasma reaction chamber and directsthe hydrocarbon-containing inflow gas into the plasma reaction chamber,wherein the microwave subsystem directs microwave energy into the plasmareaction chamber to energize the hydrocarbon-containing inflow gasthereby forming a plasma in the plasma reaction chamber, and wherein theplasma effects the transformation of a hydrocarbon in thehydrocarbon-containing inflow gas into the outflow gas products thatcomprise acetylene and hydrogen. In embodiments, thehydrocarbon-containing inflow gas can be derived from a mixed gassource, and the mixed gas source can be natural gas or a biogas; inembodiments, the hydrocarbon-containing inflow gas comprises a gasselected from the group consisting of methane, ethane, propane, andbutane, and the hydrocarbon-containing inflow gas can consistessentially of methane. In embodiments, the gas delivery subsystemcomprises a delivery conduit and a gas injector, wherein the deliveryconduit is in fluid communication with the gas injector, wherein thedelivery conduit delivers one or more gases to the gas injector, andwherein the gas injector delivers the one or more gases into the plasmareaction chamber. The delivery conduit can comprise a feed gas conveyingcircuit that delivers the hydrocarbon-containing inflow gas into the gasinjector, and the hydrocarbon-containing inflow gas can comprise methaneor can consist essentially of methane. In embodiments, the deliveryconduit comprises an additional gas conveying circuit that delivers anadditional gas into the gas injector, and the additional gas can behydrogen. In embodiments, the additional gas conveying circuit is anauxiliary gas conveying circuit that delivers an auxiliary gas into thegas injector, or the additional gas conveying circuit is a recycled gasconveying circuit that delivers a recycled gas into the gas injector.The recycled gas can comprise hydrogen, or it can comprise ahydrogen-rich reactant gas which can consist essentially of hydrogen, orthe recycled gas can consist essentially of the hydrogen-rich reactantgas.

In embodiments, the delivery conduit delivers each of the one or moregases into the gas injector through a separate pathway. In embodiments,the gas injector comprises an injector body comprising two or morecoaxially arranged and separate gas feeds, a first gas feed conveyingthe hydrocarbon-containing inflow gas into the plasma reaction chamberthrough a first set of one or more nozzles, and the second gas feedconveying the additional gas into the plasma reaction chamber through asecond set of one or more nozzles. In embodiments, at least one of theone or more nozzles is oriented at an angle to a longitudinal axis ofthe plasma reaction chamber or at an angle to a transverse axis of theplasma reaction chamber. In embodiments, at least one of the one or morenozzles is oriented at an angle to a longitudinal axis or a transverseaxis of the injector body. The combined gas flow from the first set ofnozzles and the second set of nozzles creates a vortex flow within theplasma reaction chamber. In embodiments, the plasma reaction chamber isdisposed within an elongate reactor tube having a proximal and a distalend, and the elongate reactor tube is dimensionally adapted forinteraction with the microwave subsystem. The elongate reactor tube canbe a quartz tube. The plasma reactor chamber can be disposedapproximately at the midportion of the elongate reactor tube. Inembodiments, the gas injector conveys the hydrocarbon-containing inflowgas and the additional gas into a proximal portion of the elongatereactor tube wherein the hydrocarbon-containing inflow gas and theadditional gas flow distally therefrom towards the plasma reactionchamber. The gas injector can be positioned centrally within theproximal portion, and the first set of one or more nozzles and thesecond set of one or more nozzles are oriented peripherally;alternatively, the gas injector is positioned peripherally within theproximal portion, and the first set of one or more nozzles and thesecond set of one or more nozzles are oriented centrally. Inembodiments, the microwave subsystem comprises an applicator fordirecting microwave energy towards the plasma reaction chamber, and theplasma reaction chamber is disposed in a region of the elongate reactortube that passes through the applicator and intersects itperpendicularly. The applicator can be a single-arm applicator. Inembodiments, the microwave subsystem further comprises a power supply, amagnetron, and a waveguide, whereby the power supply energizes themagnetron to produce microwave energy with the microwave energy beingconveyed by the waveguide to the applicator, and wherein the applicatordirects the microwave energy towards the reaction chamber within theelongate reactor tube, thereby forming the plasma in the plasma reactionchamber. The magnetron can produce L-band microwave energy. Inembodiments, the plasma within the plasma reaction chamber produces theoutflow gas products, and the outflow gas products flow within theplasma reaction chamber distally towards the distal end of the elongatereactor tube. The outflow products can emerge from the distal end of theelongate reactor tube to enter an effluent separation and disposalsubsystem. In embodiments, the effluent separation and disposalsubsystem can comprise a solids filter and a cold trap, and/or cancomprise an adsorption column, and/or can comprise a pressure swingadsorption system adapted for removing non-hydrogen components from aneffluent stream, and/or can comprise a temperature swing adsorptionsystem adapted for removing higher acetylenes from an effluent stream,and/or can comprise an absorption column which in embodiments can absorbacetylene, and/or can comprise a concentrated acid in an amountsufficient to oxidize higher-order hydrocarbons, and/or can comprise acatalyst suitable for converting higher-order hydrocarbons intoderivative compounds separable from the effluent stream, and/or cancomprise a condenser, and/or can comprise a gas separation membranearray which in embodiments can separate hydrogen from the effluentstream, and/or can comprise a hydrogen separation subsystem which inembodiments can be in fluid communication with the recycled gasconveying circuit wherein hydrogen collected by the hydrogen separationsubsystem is recycled into the recycled gas conveying circuit, and/orcan comprise an acetylene separation subsystem. In embodiments, thesystem further comprises a vacuum subsystem that maintains a firstreduced pressure environment for the outflow products passing throughone or more components of the effluent separation and disposalsubsystem. The vacuum subsystem can produce a second reduced pressureenvironment within the elongate reactor tube, and/or it can produce athird reduced pressure environment for the gas delivery subsystem. Inembodiments, the vacuum subsystem produces a first, second, and thirdreduced pressure environment; in embodiments, the first, second, andthird reduced pressure environments are within a range of about 30 toabout 120 Torr. In embodiments, at least one of the reduced pressureenvironments is between about 50 to about 100 Torr, or is between about60 to about 80 Torr. In embodiments, the first, second, and thirdreduced pressure environments are substantially similar. In embodiments,the system further comprises a cooling subsystem. The cooling subsystemcan comprise at least one of a water cooling subsystem and a gas coolingsubsystem. In embodiments, the gas cooling subsystem comprises anitrogen-based cooling circuit, and the nitrogen-based cooling circuitcan comprise one or more enclosures for components of the system,whereby the one or more enclosures are sealed sufficiently to enclosenitrogen gas around the components and exclude oxygen therefrom. Inembodiments, the system comprises a data management and safetysubsystem.

Further disclosed herein are methods for processing ahydrocarbon-containing inflow gas to produce acetylene gas, comprisingproviding the hydrocarbon-containing inflow gas, injecting thehydrocarbon-containing inflow gas into a reaction chamber, energizingthe hydrocarbon-containing inflow gas in the reaction chamber withmicrowave energy to create a plasma; forming gas products in the plasma,wherein one of the gas products is the acetylene gas; and flowing thegas products to exit the reaction chamber. In embodiments, thehydrocarbon-containing inflow gas is derived from a mixed gas source;the mixed gas source can be natural gas or a biogas. In embodiments, thehydrocarbon-containing inflow gas comprises a gas selected from thegroup consisting of methane, ethane, propane, and butane, and it canconsist essentially of methane. In certain practices, the method furthercomprises the step of providing one or more additional gases concomitantwith the step of providing the hydrocarbon-containing inflow gas, andthe one or more additional gases can be selected from the groupconsisting of hydrogen, nitrogen, and a recycled gas. In embodiments,the recycled gas comprises a hydrogen-rich reactant gas, which canconsist essentially of hydrogen. In certain practices, the methodfurther comprises the step of segregating acetylene gas from the gasproducts following the step of flowing the gas products to exit thereaction chamber. In certain practices, the method further comprises thestep of recycling at least one of the gas products. In embodiments, theat least one gas product can comprise hydrogen gas, or can consistessentially of hydrogen gas.

Also disclosed herein are methods for transforming ahydrocarbon-containing inflow gas into an outflow gas, comprisingproviding the hydrocarbon-containing inflow gas, directing thehydrocarbon-containing inflow gas into the gas processing system asdescribed above, and processing the hydrocarbon-containing inflow gasusing the gas processing system described above to transform the inflowgas into the outflow gas, wherein the outflow gas comprises acetylene.In embodiments, the hydrocarbon-containing inflow gas is derived from amixed gas source, and the mixed gas source can be natural gas or abiogas. In embodiments, the outflow gas further comprises hydrogen.

Disclosed herein, in addition, are metal-cutting systems, comprising thegas processing system as described above, and a storage system forcontaining the outflow gas products produced by the system; and anapparatus for metal-cutting in fluid communication with the storagesystem, wherein the apparatus draws the outflow gas products from thestorage system and ignites them for use in metal cutting. Inembodiments, the apparatus is an acetylene torch or an oxyacetylenetorch. In embodiments, the metal-cutting system further comprises ahydrogen separation system in fluid communication with the gasprocessing system as described above, wherein the outflow gas flows intothe hydrogen separation system, wherein the hydrogen separation systemseparates the outflow gas into two product streams, wherein one productstream is an acetylene-rich gas; and wherein the apparatus for metalcutting uses the acetylene-rich gas stored in the storage system as fuelfor metal cutting.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a schematic diagram showing various chemical reactionsinvolved in the conversion of methane into hydrogen, carbon, andhydrocarbon products.

FIG. 2 depicts schematically a plasma-based hydrocarbon processingsystem and component subsystems.

FIG. 3 depicts schematically a gas delivery subsystem.

FIG. 4A and 4B illustrate embodiments of gas injectors.

FIGS. 5, 6, and 7 illustrate embodiments of microwave subsystems.

FIG. 8 is a schematic showing a vacuum subsystem integrated with othersubsystems of a plasma-based hydrocarbon processing system.

FIG. 9 is a block diagram of a plasma-based hydrocarbon processingsystem and related subsystems.

FIG. 10 is a schematic diagram of a reaction chamber and its components.

FIG. 11A is a schematic diagram of a gas injector in cross-section.

FIG. 11B is a schematic diagram of a gas injector in cross-section.

FIG. 12 is a schematic diagram of a microwave subsystem.

FIG. 13 is a block diagram of a small-scale system for gas processing.

FIG. 14 is a block diagram of a small-scale system for gas processing.

DETAILED DESCRIPTION

Disclosed herein in more detail are systems and methods for convertingC₁-C₄ hydrocarbons, including unsaturated hydrocarbons and saturatedhydrocarbons such as methane (as derived from mixed gas sources such asnatural gas or biogas for example), into hydrogen, acetylene, and othercarbon-based products. In embodiments, these systems and methods usenon-thermal plasma produced by microwave energy to effect theseconversions. In embodiments, the systems and methods disclosed hereincan be optimized (“tuned”) to maximize efficient production ofacetylene, or of hydrogen, as products that can be isolated for furthercommercialization; in other embodiments, these systems and methods canbe tuned to produce a combination of these gases for specific industrialpurposes.

1. Overview

a. Non-Thermal Plasmas

Plasma, the fourth state of matter, is an ionized gas: any gas can beturned into a plasma by applying enough energy to it to create asignificant density of charged species, i.e., electrons and ions.Plasmas possess some of the properties of gases, but they differ fromthe ordinary gaseous state because they respond to both electric andmagnetic fields, properties that are due to the charged species thatexist in the plasma state. Despite having these properties, plasmas areelectrically neutral, a characteristic termed quasi-neutrality. Inaddition to the ions and free electrons from the precursor gas thatexist in the plasma, a plasma includes uncharged neutral gas species andprecursor molecules that can enter into other chemical reactions. Someweakly ionized gases do not necessarily satisfy all of the conditions ofa plasma but may still have many plasma-like qualities that influencetheir behavior. For example, many of the high-pressure plasmas used inindustrial applications fall into this category.

One of the fundamental characteristics of a plasma is its temperature.Plasmas have been used in chemical and industrial applications becausethey can generate temperatures much greater than those obtained intraditional chemical engineering processes. In a plasma, energy istransferred to electrons, which in turn transfer energy to heavierparticles through collisions. Electrons have a higher temperature thanheavier particles, and an equilibrium temperature is reached thatreflects the collisional frequency and radiative processes of thevarious particles in the plasma. Those plasmas having an electrontemperature (T_(e)) that is close to that of the heavy particles'translational temperature (T₀) are defined as thermal plasmas, with gastemperatures greater than 3,000 K. By contrast, in non-thermal plasmas,highly energetic electrons can co-exist with species havingsubstantially lower temperatures. Therefore, the translationaltemperature T₀ of the non-thermal plasma can be much lower than theelectron temperature T_(e) of the plasma—T_(e) can be close to 11,600 Kin industrial plasmas or even higher in other types of plasmas.

The energy situation in a plasma is more complex when the plasmacontains molecules (such as H₂, N₂, or CH₄) instead of just atoms. Thesemolecules have the ability to store energy in various rotational andvibrational motions, and therefore have rotational and vibrationaltemperatures associated with them. These temperatures for such plasmasgenerally lie in between the translational and electron temperature ofthe plasma, and they can affect the behavior of the plasma and itsassociated chemistry. The techniques disclosed herein are based on theability of a non-thermal plasma to transfer the major portion of theelectrical input energy to energetic electrons in the constitutive feedgas, rather than heating the gas itself. Through electron impacts,ionization, dissociation, and excitation, charged atomic and molecularspecies (e.g., electrons, ions, radicals) are generated that canparticipate in chemical reactions.

Methane is particularly resistant to chemical conversion because of itsstability: breaking the C—H bonds in methane requires an enthalpy changeof 1664 kJ mol⁻¹. Using the techniques described below, a non-thermalplasma can be produced and harnessed to break bonds in C₁-C₄hydrocarbons, including methane bonds, and create acetylene and hydrogenmolecules with high efficiency and selectivity.

b. Microwave Plasma Generation

In embodiments, the plasma used for these systems and methods is amicrowave plasma, formed by directing microwave energy at themethane-containing feed gas, as described below in more detail. Whilemethane is used as an exemplary embodiment in this description, it isunderstood that other short-chain alkanes (e.g., ethane, propane,butane) can be used as feed gases as well, either as single gas feedgases, or in combination with each other or with methane.

The microwave plasma process described herein is a gas phase process,using gaseous reactant precursors to form desired gaseous products.Because of the very fast oscillation frequency of the electric fieldrelative to the molecular and electronic collision frequencies,microwave-generated plasmas are often in a high degree ofnon-equilibrium, meaning that electron and vibrational temperatures canbe much greater than the gas temperature. In embodiments, collisionsbetween the charged species (electrons, ions) and uncharged species(molecules, atoms, particles) in the microwave plasma transfer energy:this microwave-energized plasma supports a highly reactive chemicalenvironment because of the energy contained in the plasma's freeelectrons. Because of the high degree of ionization of the precursorgas, the chemical dissociation and ionization of intermediates, and theelevated vibrational and excitational energies in the plasma, thedesired chemical reactions described below proceed rapidly andefficiently.

Without being bound by theory, microwave radiation is understood to actas follows to create a plasma from a gaseous precursor. When theprecursor gas (e.g., methane) is subjected to microwave radiation thatmeets or exceeds the dielectric strength of such gas, a free electron(present from background radiation or other sources) in the microwavefield region is able to gain enough energy from the microwave electricalfield in between collisions with neutral molecules that it can ionizeanother atom or molecule. The secondary ionized electron is subsequentlyaccelerated in a direction that is governed by the electric field ofmicrowave radiation, and it gains energy too until it causes anotherionization event. This process of ionization progresses throughout themicrowave field region until a steady state is reached. The final numberof electrons in the plasma is determined mainly by the electron lossprocesses of the plasma, such as diffusion, recombination, andattachment.

The systems and methods disclosed herein use C₁-C₄ hydrocarbons, such asmethane, as the reactant precursor gas that is subjected to microwaveradiation. Methane may be used to exemplify a reactant precursor gassuitable for use in these systems and methods.

Methane dissociation in the plasma, initiated by collisions with theenergized electrons as described above, results in the formation ofCH_(x) radicals. The major initial reaction is the breaking of the C—Hbonds in methane, with resultant formation of CH3*, CH2*, CH*,

H*, and C. These radicals can recombine to form two-carbon fragments asexemplified by the following equations:

CH₃*+CH₃*→C₂H₆

CH₂*+CH₂*→C₂H₄

CH*+CH*→C₂H₂

CH₃*+CH*→C₂H₄

CH₃*+CH₂*→C₂H_(4+H*)

CH₃*+CH*→C₂H₄

CH₃*+CH*→C₂H₂+H₂

CH₂*+CH*→C₂H₂+H*

In addition, methane can combine with various radicals to formtwo-carbon fragments as exemplified by the following equations:

CH₄+CH₃*→C₂H₆+H*

CH₄+CH₂*→C₂H₆

CH₄+CH₂*→C₂H₄+2H*/H₂ CH₄+CH*→C₂H₄

CH₄+CH*→C₂H₂ H*+H₂

Besides the illustrated reactions to form two-carbon fragments andhydrogen, higher-order hydrocarbons can be formed by recombinations ofplasma-generated radicals with each other and with the precursor gas. Asused herein, the term “higher-order hydrocarbon” refers to anyhydrocarbon having 3 or more carbon atoms, whether saturated orunsaturated, including aromatics.

Furthermore, complete dehydrogenation of methane can take place,resulting in the formation of elemental carbon and hydrogen gas.Representative reactions are show in FIG. 1. As shown in FIG. 1, anumber of exemplary reactions producing hydrocarbons are shown withinthe dotted line, while the elemental products (hydrogen and carbon) areshown outside the dotted line.

In embodiments, parameters can be optimized to maximize acetyleneformation. In other embodiments, parameters can be optimized to maximizehydrogen formation. As a general principle, for example, if the feedgases entering the plasma reaction chamber include less hydrogen ascompared to hydrocarbon input, the output will be more hydrogen formed,potentially in combination with more carbon solids. Following thisprinciple, in order to maximize hydrogen formation, a pure hydrocarbonfeed could be used, and more of the desired hydrogen would be produced,along with a quantity of carbon solids. Factors affecting productselectivity (e.g., allowing the preferential formation of acetylene overother species, or allowing the preferential formation of hydrogen overhydrocarbon products) include, without limitation, the identity of thereactant precursor gas, the addition of other gases to the system, theflow rate of any gases entering the system, the temperature and pressurein the reactor system, the amount of microwave power and flow geometryused to create the plasma, the energy density in the reaction zone, thearrangement of the electrical field surrounding the plasma, and reactorvessel geometry and dimensions. In embodiments, static electric andmagnetic fields can be employed to influence the behavior of the plasmaand hence the product selectivity.

c. Precursor Gases

For the systems and methods disclosed herein, C₁-C₄ alkane hydrocarbons(for example, methane, ethane, propane, and butane) or other hydrocarbongases can be used alone or in combination with other gases as precursorgases. In an embodiment of these systems and methods, methane is themain precursor gas. In embodiments, it can be combined with hydrogenand/or nitrogen as it enters the plasma reaction chamber, forming asingle gas mixture that is energized to the plasma state. Inembodiments, methane enters the plasma reaction chamber through its ownset of nozzles, while other gases (such as hydrogen and/or nitrogen) areadded to the plasma reaction chamber separately, through a different setor sets of nozzles. Methane can be used in a pure state, or it can beintroduced into the system as a component of a commercially availablegas stream.

Mixed gas sources such as natural gas or biogas are particularlyadvantageous sources of this precursor gas. As used herein, the term“biogas” refers to a mixed gas produced by the anaerobic decompositionof organic waste material in various natural or manmade environments;the term “biogas” includes all those natural or man-made environments inwhich such gas-producing anaerobic decomposition can take place, e.g.,landfills, manure holding ponds, municipal waste sites, sewage treatmentfacilities, agricultural waste sites, permafrost decay, and the like.Biogas as collected or retrieved from those sites can be treated orupgraded to increase its methane content and to remove impurities, sothat it becomes especially suitable as a precursor gas for the systemsand methods disclosed herein.

Biogas, produced from raw materials such as municipal waste,agricultural waste, plant material, sewage, manure, food waste or othernatural or manmade organic sources, is typically formed in a closedsystem via the anaerobic digestion or fermentation of the organicmaterial. The first stage of this process is hydrolysis, in which theinsoluble organic polymers are broken down into sugars and amino acidsthat serve as substrates for the activity of the anaerobic acidogenicbacteria. In a second stage, these bacteria convert the sugars and aminoacids into carbon dioxide, hydrogen, ammonia, and organic acids; theacidogenic bacteria further convert the organic acids into acetic acid,ammonia and carbon dioxide. As a third stage, a separate population ofanaerobic bacteria, the methanogens, convert these fermentation productsinto methane and carbon dioxide. Biogas, containing a mixture of methaneand carbon dioxide along with gaseous byproducts such as hydrogensulfide, can be collected and treated to remove carbon dioxide and theundesirable gaseous products, leaving a gaseous mixture with a highconcentration of methane that is suitable for energy production or forfurther processing. Methane in biogas is concentrated using a process ofbiogas upgrading, resulting in a product that has similar performancecharacteristics to fossil-derived natural gas.

Processes such as water washing, adsorption, membrane separation, aminegas treatment, and the like, can be used for biogas upgrading. Upgradingprocesses can advantageously be carried out to remove oxygen from thebiogas before it is used as a gas source. Oxygen in the feed gas canrender it vulnerable to combustion; moreover, oxygen can corrodeequipment used in the plasma-based hydrocarbon processing system asdisclosed herein. Furthermore, under certain circumstances, oxygenremoval may be necessary to meet regulatory standards or other purityrequirements. A number of oxygen removal technologies are suitable foruse with biogas. As an example, oxygen can be reacted with a reducedmetal species, thus oxidizing the metal and consuming the oxygen. Theoxidized metal species will then be regenerated back to the active formby reducing the metal species by passing a hydrogen or carbon monoxidecontaining gas stream over the metal species, generating water or carbondioxide, respectively. Metal species such as palladium or nickel couldbe used to catalytically combust oxygen at >500° F. with hydrocarbonspecies mixed with the O₂. As another approach, solid scavengers can beused in a disposable fashion to trap oxygen. For example, Fe₂S₃ canreact with three molar equivalents of molecular oxygen to form rust andelemental sulfur. As yet another approach, oxygen can be separated fromother gases by molecular sieves, such as 5A or 13X molecular sieve,similar to the technology seen in air separation units (ASUs). Otherupgrading processes for biogas would be available to skilled artisansusing no more than routine experimentation. Upgraded biogas can reach apurity and quality similar to the natural gas in U.S. pipelines, and canbe used for the same purposes.

Natural gas as extracted from the earth is predominantly methane, makingit a useful source of precursor gas for these systems and methods.Typically, it also includes higher-order hydrocarbons such as ethane,propane, butane, and pentane, along with non-hydrocarbon impurities. Thetable below (Table 1) illustrates an exemplary composition of naturalgas.

TABLE 1 Methane CH₄ 70-90% Ethane C₂H₆  0-20% Propane C₃H₈ Butane C₄H₁₀Carbon Dioxide CO₂  0-8% Oxygen O₂  0-0.2%  Nitrogen N₂  0-5% Hydrogensulfide H₂S  0-5% Rare gases Ar, He, Ne, Xe Trace Source:http://naturalgas.org/overview/background

Natural gas is generally processed to remove most of the non-methanecomponents before it is made available for commercial or residentialuse, so that it is almost pure methane when it is reaches the consumer.As an example, natural gas available commercially can include about 96%methane. While an extensive system of pipelines exists in the UnitedStates to bring natural gas to consumer markets after it has beenstripped of its impurities, much natural gas is found in areas that arefar from these markets and far from the pipeline infrastructure (oftentermed remote or “stranded” natural gas). In embodiments, the systemsand methods disclosed herein can be used in situ, for example at thelocation of the stranded natural gas, to convert it into acetylene andother useful products; these systems and methods accordingly offer acost-effective way to utilize this stranded natural gas as a resource.

2. Systems and Subsystems

In embodiments, the plasma-based hydrocarbon processing system asdisclosed herein can comprise six subsystems: 1) a gas deliverysubsystem, 2) a microwave subsystem, 3) a vacuum subsystem, 4) a coolingsubsystem, 5) an effluent separation and disposal subsystem, and 6) adata management and safety subsystem. These subsystems are described inmore detail below. The integration of these subsystems is shownschematically on FIG. 2. Desirable outputs from these subsystems andmethods can include a high degree of methane conversion, and a highdegree of acetylene selectivity and/or a high degree of hydrogenselectivity.

As shown schematically in FIG. 2, a plasma-based hydrocarbon processingsystem 200 provides for the conversion of one or more inflow gases 202,204, and 208 into a mixture of gaseous products contained in an outflowstream 212 emerging from a plasma reaction chamber 214, where the plasmareaction chamber contains the plasma that has been generated by amicrowave subsystem 218. In the depicted embodiment, a hydrocarboninflow gas 202, such as methane, enters the plasma reaction chamber 214separately from the hydrogen-containing inflow gas 208 that is producedfrom a recycling of a certain fraction of the outflow stream 212. Anoptional auxiliary gas 204 such as nitrogen can be introduced separatelyas shown, or it can be mixed with one or both of the other inflow gases202 and 208. The various inflow gas streams and their direction into theplasma reaction chamber 214 are encompassed by the gas deliverysubsystem 210. The gas delivery subsystem 210 is responsible forproducing the appropriate proportions of inflow gases and controllingtheir flow rates. Once the inflow gases enter the plasma reactionchamber 214, they are energized by microwaves produced by the microwavesubsystem 218, which creates a plasma state within the plasma reactionchamber 214. An outflow stream 212 carries outflow (or “produced”) gasproducts including acetylene, hydrogen, and a mixture of unreactedmethane and higher-order hydrocarbons. Carbon solids can be entrained bythe outflow gas stream 212. An effluent separation and disposalsubsystem 220 allows for the separation of waste components from theoutflow stream 212 so that they can be disposed of, and further allowsfor the separation of desirable components into discrete streams asnecessary for further commercialization or for reintroduction into theplasma reaction chamber 214 as an inflow gas 208. For example, acetylene224 can be separated from the outflow stream 212 in theseparation/disposal subsystem 220, and it can be used commercially. Inembodiments, for example, the acetylene can be further purified for usein chemical reactions. In other embodiments, the acetylene can befurther processed, either to form other compounds or to form elementalcarbon for other uses or for disposal. In embodiments, the carbon solidsentrained by the outflow gas stream 212 can be removed by theseparation/disposal subsystem 220 as a discrete product or wastematerial 222. In the depicted embodiment, a recycled stream 228 that ispredominately hydrogen emerges from the separation/disposal subsystemand is recycled back into the plasma reaction chamber 214 as an inflowgas 208. In other embodiments, a portion or the entirety of hydrogenproduced by the reactor can be separated from the outflow stream 212 andcommercialized separately. In yet other embodiments, the separation ofoutflow stream 212 components proceeds differently: for example, carboncan be separated entirely, with a mixed hydrogen and hydrocarbon gasstream being segregated for commercialization or other uses. Theseparation/disposal subsystem can be configured to segregate singlegases or gas mixtures in accordance with specific gas processing goals.As shown schematically in FIG. 2, a vacuum subsystem 230 surroundscertain system components to maintain them at a low pressure. A coolingsubsystem (not shown) provides appropriate cooling for each systemcomponent.

In embodiments, a number of system parameters can be modified tooptimize hydrocarbon (e.g., methane) conversion rate and acetylene orhydrogen selectivity, including input gas flow rate (SLM), inputpressure, and power per converted hydrocarbon (e.g., methane). Table 2shows the effect of varying these parameters. A useful metric forcomparing results of different system parameters is efficiency,calculated as the energy used per molecule of methane converted(eV/CH₄). This metric is easily applied to both industrial uses, such asproduction cost per kg of product, and scientific uses, such ascomparing against bond strengths and calculating thermodynamicefficiency.

TABLE 2 1 2 3 Reactor I.D. (mm.) 108 108 108 CH₄/H₂/N₂ Feed 383/460/38367/550/37 338/676/34 flow (SLM) Pressure (Torr) 40 42 52 eV/CH₄ 3.904.07 4.42 Effluent (SLM) 1226 1285 1353 CH₄/H₂/N₂/C₂H₂ 1.6/81.5/3.1/13.81.4/83.1/2.9/12.6 1.2/85.2/2.6/11 Effluent (%) C₂H₂ Selectivity 93 93 93(%)

a. Gas Delivery Subsystem

In embodiments, a gas delivery subsystem is constructed to direct inflowgases into the plasma reaction chamber. The gas delivery subsystemcomprises two components, the delivery conduit and the gas injector.Included in the description of this subsystem are further descriptionsof (i) gases fed into the reactor (inflow gases); (ii) the deliveryconduit for conveying inflow gases into the plasma reaction chamber,where the delivery conduit includes one or more separate circuits (or“conveying circuits”) for gas flow, and where the conveying circuits caninclude a main feed gas conveying circuit, auxiliary gas conveyingcircuits for additional gases besides the main feed gas, and/or arecycled gas conveying circuit to allow return of one or more producedgases (e.g., hydrogen) to be used as inflow gases for subsequentreactions, and (iii) the gas injector assembly in fluid communicationwith the delivery conduit and its component conveying circuits thatintroduces component inflow gases into the plasma reaction chamberitself

i. Inflow Gases

Inflow gases can comprise precursor reactant gases such as C₁-C₄ alkanehydrocarbons in various combinations. Precursor reactant gases are thosethat provide hydrogens or carbons for further reactions in the plasmastate. In embodiments, the inflow gases are methane and hydrogen, withnitrogen optionally combined with the methane. In certain embodiments,methane and hydrogen are reactants. The proportions of reactant gases,along with the optional nitrogen additive, can be varied empirically tooptimize the product profile and yield.

Inflow gases used by the plasma-based hydrocarbon processing system canbe supplied directly from feed tanks, feed lines, and/or throughrecycling. As used herein, the term “inflow gas” means any gas that isadded to plasma reaction chamber within which the plasma is formed. Aninflow gas may be a reactant gas such as methane or hydrogen, which istransformed by the plasma state into various products, as described inFIG. 1. An inflow gas may be an auxiliary additive gas such as nitrogen.An inflow gas can be supplied from external gas sources called “feedlines,” or from intrasystem recycling, wherein a gas produced by thesystem is reintroduced in whole or in part into the plasma reactionchamber for subsequent reactions.

An inflow gas entering the system via an external gas source or feedline can be derived from a gas reservoir such as a storage tank, or itcan be derived from an extrinsically situated flowing gas lines such asa mixed gas source line (e.g., a natural gas line or biogas line). Inembodiments, the inflow gas contains solely (or substantially only) thereactants methane and hydrogen, with no deliberately added additionalgaseous additives. The methane in the inflow gas can be obtained as acomponent of a more complex flowing gas mixture such as natural gas orbiogas. In embodiments, methane and, optionally nitrogen, are fed infrom feed lines (i.e., storage tanks or flowing gas lines), whilehydrogen can be fed in from a storage tank or it can be recycled fromthe product stream and directed back into the reactor.

A recycled gas stream used for intrasystem recycling is an effluent(i.e., outflow gas) from the plasma reaction chamber, optionallyseparated into various component gases, with some or all of this gas orthese gases reintroduced into the plasma reaction chamber. Inembodiments, the hydrogen in the outflow gas products stream isseparated from other gases and is recycled in a purified form. Inembodiments, a hydrocarbon inflow gas is introduced into the plasmareaction chamber via a flowing gas feed line, for example a natural gasline or biogas line, while hydrogen is introduced into the plasmareaction chamber separately from the hydrocarbon inflow; this hydrogencan be derived in whole or in part from a recycled gas stream.

In embodiments, the recycled gas can comprise a hydrogen-rich reactantgas, wherein hydrogen is the main component, with some hydrocarbons alsopresent that are capable of reactions. A hydrogen-rich reactant gas canconsist essentially of hydrogen, i.e., can include about 95% hydrogen orgreater, or about 96% hydrogen or greater, or about 97% hydrogen orgreater, or about 98% hydrogen or greater, or about 99% hydrogen orgreater. In embodiments, the hydrogen-rich reactant gas comprises about90% of the recycled gas or more, or about 91% of the recycled gas ormore, or about 92% of the recycled gas or more, or about 93% of therecycled gas or more, or about 94% of the recycled gas or more. Inembodiments, the recycled gas consists essentially of the hydrogen-richreactant gas, i.e., the hydrogen-rich reactant gas comprises about 95%of the recycled gas or more, or about 96% of the recycled gas or more,or about 97% of the recycled gas or more, or about 98% of the recycledgas or more, or about 99% of the recycled gas or more. In embodiments,the recycled gas comprises a non-reactant gas such as nitrogen inaddition to the hydrogen-rich reactant gas. In embodiments, theremainder of the recycled gas apart from the hydrogen-rich reactant gasis nitrogen. In other embodiments, nitrogen is added as a separateauxiliary gas, apart from its presence or absence in the recycled gas.Volumes of hydrogen and nitrogen used in the system can be expressed inrelation to the total methane flow. For example, the following ratio ofinflow gas feeds can be used: 1:0-3:0.1 methane: hydrogen: nitrogen; inother embodiments, the following ratio of inflow gas feeds can be used:1:1-2:0.1 methane: hydrogen: nitrogen. In embodiments, similar ratios ofmethane and hydrogen can be used in the absence of nitrogen. In anembodiment, a methane flow into the reactor of 300-400 SLM(approximately 11-14 SCFM) can be used. In an embodiment, a methane flowof about 380 SLM (13.4 SCFM) can be used. In embodiments, these flowsare suitable for a reactor power of 100 kW.

In embodiments, the amount of hydrogen entering the reactor can bevaried in order to select for more or less acetylene production.Increasing the amount of hydrogen entering the reactor increases theamount of this gas available for reacting with methane, therebyimproving the conversion selectivity for acetylene production anddecreasing the amount of undesirable soot build-up. In embodiments, anincreased amount of hydrogen entering the reactor decreases the amountof ethylene in the outflow, as compared to acetylene.

In embodiments, hydrogen is provided from hydrogen cylinders. In otherembodiments, hydrogen can be provided by recycling hydrogen that isproduced by the overall system: in other words, hydrogen produced from aC₁-C₄ hydrocarbon feedstock such as methane in the plasma reaction canbe reused as a reactant. In certain embodiments, a recycled gasconveying circuit that conveys hydrogen as an inflow gas back into thesystem can be combined with a separate inflow source of hydrogen, forexample from a hydrogen feed tank to tune the input of this gas. Thisapproach can be advantageous at certain times during the productioncycle, for example at system start-up when no recycled hydrogen has yetbeen produced, or to keep hydrogen inflow at a constant level despitevariations in hydrogen produced during recycling.

In an embodiment, the gas delivery subsystem can be precharged, forexample, at system start-up, to balance the mixing of gases and toharmonize the gas flow with the microwave energy. First, the system canbe evacuated and set at a near-vacuum pressure. Second, the system canbe filled from an external source of hydrogen, either backfilled viahydrogen introduced retrograde into the recycled gas conveying circuit,or front-filled from a separate hydrogen inflow line. Third, a C₁-C₄hydrocarbon (e.g., methane) or C₁-C₄ hydrocarbon/nitrogen mixture can beadded as an inflow gas, with flows measured by flowmeters. With thesystem thus precharged with appropriate gases, the reactor can beenergized, and the inflow gases can be processed. As the inflow gasesare processed in the plasma reaction chamber, hydrogen is generated inthe outflow gas products stream, along with other gas products. Hydrogencaptured from the outflow gas products stream then can be recycled intothe system, while at the same time the exogenous hydrogen inflow isdecreased. This balancing of extrinsic and intrinsic hydrogen inflows(from external feed lines and from recycling) can facilitate a smoothstart-up procedure for the overall system.

In embodiments, methane is the main component of the hydrocarboncontaining inflow gas for the plasma-based hydrocarbon gas processingdescribed in these systems and methods. In embodiments, methane can beintroduced from gas cylinders, from pipelines, or from an inflow of amixed gas (e.g., natural gas or biogas) as described previously. A setof compressors can be used, so that methane is introduced at a correctpressure, for example at a feed pressure of at least about 2 atm. Ifnatural gas or biogas is used to provide the methane feed gas, theamount of available methane can be monitored, for example by using abenchtop gas chromatograph, and the impurities in the natural gas can beidentified and removed. For example, if the natural gas or biogas feedcontains sulfur, it can affect the purity of the acetylene productstream; such an impurity must be removed before processing. Variousimpurities that are commonly found in natural gas or biogas (e.g.,carbon dioxide, mercaptans, hydrogen sulfide, and the like) can beremoved with a series of pre-scrubbers, where the type of scrubberselected depends on the impurity to be removed.

Desirably, a mixed gas comprising methane can include a highconcentration of methane, so that it is substantially free of impuritiesor other gases. Natural gas derived directly from a natural sourcewithout commercial treatment can contain about 90% or greater ofmethane. However, natural gas that is processed to be availablecommercially, or equivalently treated biogas, can be substantially freeof non-methane gases and impurities. A hydrocarbon-containing inflow gasfrom such a source is deemed to consist essentially of methane, whichterm refers to an inflow gas containing about 95% of methane or greater.Such a gas, consisting essentially of methane, can contain, for example,about 95% methane or greater, or about 96% methane or greater, or about97% methane or greater, or about 98% methane or greater, or about 99%methane or greater. Gases provided from natural sources such as in situnatural gas (as found in wells prior to processing) or such as biogasmay contain lesser amounts of methane, but they can be pretreated foruse as a hydrocarbon-containing inflow gas so that such gases havehigher concentrations of methane; in embodiments, such pretreated gasesconsist essentially of methane when used as hydrocarbon-containinginflow gases for these systems and methods.

In embodiments, other auxiliary gases can be used as components of oradditives to the inflow gas stream, for example additives such asnitrogen, carbon dioxide, and/or other reactive or inert gases. In anembodiment, nitrogen can be optionally used as a component of the inflowfeed gas; it can also be used as a sealing gas for the vacuum pumps, asdescribed below. In an embodiment, the inflow feed gas contains about10% nitrogen, although this amount may be varied or tuned to optimizeefficiency and selectivity for acetylene production; in otherembodiments, nitrogen may be present in amounts ranging from about 0% toabout 10%, with the nitrogen either deliberately added or extraneouslypresent, for example as a minor component adventitiously found the feedgas. In other embodiments, no additional nitrogen is included. Inaddition to its use as an inflow gas component, nitrogen in gas andliquid form can be used as a part of the cooling subsystem to coolvarious components and provide a nitrogen “buffer” around the reactor,as described below. Carbon dioxide can be included as a separatecomponent of the inflow gas, or it can be mixed into the reactoreffluent to serve as an internal standard for gas chromatographicanalysis of that effluent. In an embodiment, carbon dioxide is added tothe effluent in the amount of 30% of the methane feed in order toachieve good precision in downstream gas chromatography measurements.Other auxiliary gases may be used as inflow gases along with thereactant gases, for example helium for gas chromatography and argon.

ii. Gas Delivery Conduit

The gas delivery conduit conveys the various inflow gases (includingreactant gases, additive or auxiliary gases, and recycled gases) intothe gas injector; the gas injector delivers the various inflow gasesinto the plasma reaction chamber. The gas delivery conduit containsconveying circuits dedicated to specific gas streams: the feed gas iscarried within the feed gas conveying circuit, additional gases arecarried by one or more additional gas conveying circuits, recycledgas(es) are carried by one or more recycled gas conveying circuits. Inembodiments, these systems and methods use a hydrocarbon-bearing inflowstream as a main gas feed, for example, a methane stream or a mixed gasstream (e.g., natural gas or biogas), with the main gas feed beingcarried by the feed gas conveying circuit. In embodiments, additionalgas streams can also pass through the gas delivery conduit in additionto the main gas feed, adding inert gases such as nitrogen, and/or addingreactants such as hydrogen as separate streams via their designatedconveying circuits. Furthermore, in embodiments, a recycled gas streamcan be added to the mix through a recycled gas conveying circuit, asdescribed in more detail below; a recycled gas stream can containhydrogen as the predominant component, along with small quantities ofunreacted methane and other hydrocarbon components. In embodiments, eachconveying circuit is in fluid communication with the gas injectorassembly and conveys its gas separately into the gas injector assembly,for example through a dedicated nozzle, valve, or conduit.

A schematic diagram of an embodiment of a gas delivery subsystem 300 inaccordance with these systems and methods is shown in FIG. 3. As shownin this Figure, a hydrocarbon-bearing inflow gas stream 302 is combinedwith a hydrogen-bearing inflow gas stream 304 and an optional auxiliarygas stream 308 to enter the plasma reaction chamber 310.

In the depicted embodiment, the three gas streams enter through a gasinjector 312 (described below in more detail) which disperses thevarious flows in directions and with velocities such that a vortexintermingling 314 of the three separate flows is produced within theplasma reaction chamber 310. The intermingled gases in the vortexintermingling 314 enter a reaction zone 318 of the plasma reactionchamber 310, where they are energized by the microwave energy producedin the microwave subsystem 322 to form the plasma 320 within thereaction zone 318 of the plasma reaction chamber 310. In the depictedembodiment, the inflow gases 302, 304 and 308 each enter the gasinjector 312 as separate streams through separate inlets, and eachenters the plasma reaction chamber 310 through its own outlet from thegas injector. The flow direction, flow velocity and flow rate from eachoutlet is oriented so that it produces the vortex intermingling 314 ofthe gases within the plasma reaction chamber 310.

Inflow gases can be introduced into the plasma reaction chamber inconstant or variable flow patterns, and in continuous flow patterns ordiscontinuous flow patterns, and in any combination of these patterns.In embodiments, a variable flow pattern can be regular or irregular inits variability, and it can include intermittent pulses or surges offlow superimposed on an underlying wave form describing the flowpattern. A sinusoidal flow pattern would be an example of a variableflow pattern, as would a stepwise or “boxcar” flow pattern using squarewaves to delineate different amounts of flow. In embodiments, thesevariable flow patterns can include periods where there is no flow, sothat the variable flow pattern would be discontinuous. In embodiments,gases can be introduced through all of the inlets simultaneously, orgases can be introduced through different inlets at different times.Gases can be introduced at different flow rates and at different flowpatterns at each inlet. For example, a feed gas can be introducedcontinuously with a constant flow pattern, while one or more auxiliarygas streams can be introduced sporadically, i.e., discontinuously. Or,for example, the feed gas can be introduced discontinuously (i.e., withinterruptions in its inflow), with one or more auxiliary gasesintroduced variably and/or discontinuously so that the auxiliary gasesare flowing while the feed gas is not. Or, as another example, a feedgas can be introduced continuously with a continuous flow pattern, whileone or more auxiliary gas streams can be introduced continuously, butwith a different flow pattern than the feed gas. Other combinations ofcontinuous/discontinuous patterning and flow pattern variability can bearranged to accomplish specific gas processing goals, for example, todecrease soot formation in the plasma reaction chamber, or to increaseacetylene selectivity, or to allow for intermittent cleaning of thereaction tubing interior.

As previously described, gases that are energized into the plasma stateundergo a spectrum of reactions, so that a hydrocarbon feed gas istransformed into other hydrocarbons plus hydrogen. FIG. 3 shows anoutflow stream 324 emerging from the plasma 320 that contains thedesired hydrocarbon product or products, certain extraneous hydrocarbonproducts, and hydrogen gas. The components of the outflow stream 324 areseparated from each other by means of the effluent separation/disposalsystem 328, described previously.

iii. Gas Injector

The gas injector introduces the various inflow gas streams into theplasma reaction chamber through a plurality of inlets. In embodiments,the gas injector containing the flow channels for the various inflow gasstreams can be printed out of a high temperature resin. It can bedeployed within or is disposed in fluid communication with the reactorat a variable distance from the plasma reaction chamber within thereactor, where the term “plasma reaction chamber” refers to the regionwithin the reactor where the microwave energy encounters the feed gasstreams. In an embodiment, the gas injector can be positioned at theproximal end of the reactor, permitting antegrade gas flow from proximalto distal along the long axis of the reactor. In other embodiments, thegas injector can be positioned at the distal end of the reactor, or canbe positioned at any other location along the long axis of the reactor.In embodiments, the gas injector is positioned centrally within thereactor tube, with gas flow directed peripherally. In other embodiments,the gas injector is positioned peripherally within the reactor tube,with gas flow directed centrally. Gas flow exiting the nozzles can beaimed at any angle along the long axis of the tube, so that gas can flowproximally or distally in an axial direction. The nozzles can bearranged to yield symmetric or asymmetric vortex flow.

In embodiments, the inflow gas flows can be aimed by the gas injector soas to create a spiral or vortical gas flow, which assists with mixingthe various gas streams.

The gas injector is configured to provide a separate nozzle or port foreach inflow gas stream as it enters the reactor. The vortical flow canbe produced from a gas injector device disposed centrally in the reactorwith two or more nozzles or ports, where each inflow gas is separatelydelivered through its own subset of the one or more nozzles or ports. Inan embodiment, these nozzles or ports, located centrally within thereactor, can be aimed peripherally, and can be angled to create thedesired gas flow pattern. In other embodiments, vortical flow can beproduced by gases flowing into the reactor through a gas injector havingtwo or more nozzles or ports arrayed along the periphery of the reactor,where each inflow gas is separately delivered through its own discretesubset of the two or more nozzles or ports. In embodiments, the vorticalflow serves to confine the plasma toward the interior region of thereactor. Additional vortex flow configurations, such as reverse vortexflow, can also be employed, as would be understood by those skilled inthe art.

FIGS. 4A and 4B depict an embodiment of a gas injector that iscompatible with these systems and methods. FIG. 4A shows a transversecross-section of the proximal part of the reaction chamber 402 of aplasma reactor 400, within which the gas injector 404 is centrallylocated; the approximate location of the depicted cross-section in FIG.4A is shown as Line A in FIG. 3. The gas injector 404 shown in this FIG.4A encases two coaxial but separate gas flows, a central gas flow 408and a secondary gas flow 410. The central gas flow 408 contains one gas,for example the main feed gas that can contain methane, the primaryreactant. The secondary gas flow 410 contains a separate and distinctgas, for example an additional gas such as hydrogen or an auxiliary gas;this gas can also be a recycled gas such as hydrogen. Alternatively, thecentral gas flow 408 can contain the additional gas, while the secondarygas flow can contain the main feed gas. In other embodiments (notillustrated), the recycled gas flow can be maintained in a separatecoaxial chamber distinct from a flow channel for an auxiliary gas, witheach flow channel having its own set of one or more gas nozzles enteringthe plasma reaction chamber 402. For the injector design depicted inFIG. 4A, the central gas flow 408 exits the gas injector 404 centrallythrough a central gas nozzle 412 aimed distally and seen here only incross-section, while the secondary gas flow 410 exits the gas injector404 through gas nozzles 412 a and 412 b, which are aimed peripherally.As shown in this Figure, the secondary gas nozzles 412 a and 412 b aredirected at an angle that allows the secondary gas flows 414 a and 414 bto enter the plasma reaction chamber 402 to form a gas vortex within thereactor 400.

FIG. 4B shows a longitudinal section of an embodiment of a gas injector450, incorporating the principles illustrated in FIG. 4A. The gasinjector 450 depicted in FIG. 4B shows the coaxial arrangement of thecentral gas flow 452 surrounded by the secondary gas flow 454. The gasinjector 450 is positioned centrally within the reactor (not shown inthe Figure), and the gas flows from the central gas flow 452 and thesecondary gas flow 454 exit the gas injector 450 to flow into thereactor. The secondary gas nozzles 458 a and 458 b can be arranged atangles (as seen in FIG. 4A), so that the secondary gas exiting thesenozzles is aimed to create a vortex flow. As well, the gas exiting theprimary gas nozzle 460 can be directed to create or to contribute to avortex flow. In embodiments, the vortex flow created in the reactor 400by the gas injector 450 permits gas mixing, which in turn can optimizethe exposure of the gas streams to the plasma.

b. Microwave Subsystem

In embodiments, the microwave subsystem comprises the various componentsused to generate, guide, and apply microwave power to form thenon-thermal plasma that transforms the feed gas into its products.

A schematic diagram for an embodiment of a microwave subsystem is shownin FIGS. 5 and 6, described in more detail below. FIG. 5 provides anoverview of the subsystem's components. As shown in FIG. 5, anembodiment of the microwave subsystem 500 includes a power supply 502, amagnetron 504, a waveguide assembly 508, and an applicator 510, with themicrowave energy produced by the magnetron 504 encountering the inflowgas in a plasma reaction chamber 512 within an elongate reactor tube 514(seen here in cross-section) to create the plasma. The reactor tube 514can be made of quartz, as is described below in more detail. In anembodiment, the power supply 502 requires 480 V, 150 A of AC electricalpower to generate 20 kV, 5.8 A of low ripple DC power with an efficiencyof 96% to energize the magnetron. In an embodiment, the magnetron 504,also rated at 100 kW, produces microwave power at 83-89% efficiency. Inembodiments, the microwaves produced are in the L-band, having afrequency of 915 MHz.

As shown in this Figure, the microwaves enter a waveguide assembly 508that directs them to the applicator 510, which in turn directs themicrowaves to the plasma reaction chamber 512 in the reactor tube 514.In the depicted embodiment, the waveguide assembly 508 comprises twocirculators 518 and 520, which direct the microwaves towards theapplicator 510 and which prevent reflected microwave power from couplingback into the magnetron 504 and damaging it. Each circulator 518 and 520contains a ferrite array 516 and 526 respectively that deflectsreflected microwaves in order to direct them towards the applicator 510and plasma reaction chamber 512, as described below in more detail. Eachcirculator 518 and 520 has its respective water load 522 and 524 at itsend to collect the reflected microwaves. As depicted, the secondcirculator 520 includes a power tuner 528 that steps down power using athree-stub tuner 530 in the arm that is distal to its junction with theapplicator. In the arm of the second circulator 520 that interfaces withthe applicator 510, a three-stub tuner 532 is arranged distal to thedual-directional coupler 534; this arrangement is intended to minimizemicrowave reflection and optimize the microwave energy directed into theapplicator 510. A quartz window 538 is inserted between the secondcirculator 520 and the applicator 510 to prevent arcing. When the plasmais off and the microwaves are on, a standing wave is set up in theapplicator 510 between the three-stub tuner 532 and a sliding shortingplate 540 on the end of the applicator 510 such that the electric fieldis sufficient to initiate breakdown of the feed gases in the reactortube 514 that contains the plasma reaction chamber 512. The reactor tube514 runs through the broad wall of the applicator 510 but is not indirect contact with the microwave waveguide 508. Once the initiation ofthe plasma state is achieved, the three-stub tuner 532 can then beadjusted to match the impedance of the incoming microwave signal to theplasma-loaded applicator 510. Microwave energy entering the applicator510 is tuned to peak at the center of the plasma reaction chamber 512,using the shorting plate 540 as needed to change the dimensions of thecavity within which the plasma is formed.

To optimize the power for producing the plasma, it is desirable to matchthe impedance of the waveguide 508 to the impedance of the applicator510 in the presence and the absence of the plasma. Plasma impedance isdynamic however, and can change based on the operating pressures, gasflows, and gas compositions in the plasma reaction chamber 512. Inembodiments, the microwave subsystem can be equipped with a standardthree-stub autotuner 532, which has three metal stubs inserted into thewaveguide. The depth to which each of these stubs is inserted into thewaveguide alters the phase of the microwaves entering the reactor 510and allows for power matching into the plasma. Microwave power and phasemeasurement in the autotuner 532 allow the autotuner 532 to modify stubdepth algorithmically, so that reflected power (i.e., the power notabsorbed by the plasma), is minimized. In embodiments, a dualdirectional coupler 534 with attached power diodes (not labeled) can beincluded, to measure forward and reflected power in the subsystem.

The coupler 534 can be fitted with two small holes that couplemicrowaves with a known attenuation to the diodes, which convert themicrowave into a voltage. In embodiments, reflected power is less than1% of total microwave power sent into the system. In embodiments, themicrowave applicator 510 is a single-mode resonant cavity that couplesthe microwaves to the flowing gas feed in the plasma reaction chamber512. A sliding electrical short 540 can be built into the applicator 510to change total cavity length. In embodiments, the plasma for the 100-kWdemo unit can generate upwards of 10 kW of heat, which can be removedvia water and gas cooling subsystems.

The plasma is created in the plasma reaction chamber 512 within theelongate reactor tube 514. In embodiments, the reactor tube 514 cancomprise a long aspect ratio fused quartz tube, with an outer diameterbetween about 30 and about 120 mm, a length of approximately 6 ft, and athickness varying from about 2.5 to about 6.0 mm. In an embodiment, thereactor tube can have an outer diameter of 50 mm, or an outer diameterof 38 mm. In embodiments, tube sizes can have an outer diameter (OD) andcorresponding inner diameter (ID) of 120/114 mm OD/ID, or 120/108 mmOD/ID, or 80/75 mm OD/ID, or 50/46 mm OD/ID, or 38/35 mm OD/ID. Inembodiments, the reactor tube 514 has a consistent diameter throughoutits length. In other embodiments, the reactor tube 514 can have avarying diameter, with certain portions of the tube 514 having a smallerdiameter, and other areas having a larger diameter. In embodiments, atube can have an outer diameter of about 50 mm at the top and about 65mm at the bottom. In embodiments, the tube can have a narrower diameterat a preselected portion of the tube, for example, approximately in themiddle of the tube. Quartz is advantageous as a reactor tube 514material because it has high temperature handling, thermal shockresistance, and low microwave absorption.

FIG. 6 shows, in more detail, a microwave subsystem 600, such as wasdepicted in FIG. 5, and the paths of microwave energy 605, 607, and 615flowing therein; in FIG. 6, certain features of the microwave subsystem600 are shown schematically but, for clarity, were not labeled as theywere in FIG. 5. As shown in the embodiment depicted in FIG. 6, microwaveenergy, generated by the magnetron 604, is directed forward along aforward energy path 605 from the magnetron 604 to the distal end of thewaveguide assembly 608, from which it is reflected along an antegrade(forward) reflected path 607. The direction of the antegrade (forward)reflected path 607 is shaped by its encounter with the ferrite array 626in the second circulator 620, which deflects the reflected microwaves607 towards the applicator 610 and the plasma reaction chamber 612.Microwaves may also be reflected retrograde from the applicator 610along a retrograde (reverse) reflected path 615, which passes backwardsthrough the second circulator 620 into the first circulator 618, wherethe microwaves in this path 615 are collected by the water load 622within the first circulator 618. The retrograde (reverse) reflected path615 is deflected by the ferrite array 626 in the second circulator 620,and then by the ferrite array 616 in the first circulator 618 toestablish its final direction. In an embodiment, forward power in thesystem is approximately 25 kW, with reflected power 1% of this or less,with the goal of 0% reflected microwave energy. In embodiments, theforward power in the system is approximately 30 kW; in otherembodiments, the forward power in the system is approximately 100 kW. Inyet other embodiments, forward power levels of about 8 kW, about 10 kW,or about 19-20 kW can be employed. In embodiments, the system canadvantageously encompass a forward power at levels less than about 100kW.

In an embodiment, the microwave subsystem includes a single arm pathwaytowards the plasma reaction chamber, as depicted in FIG. 5 and FIG. 6.In other embodiments, a double-arm applicator pathway can be employed,as shown below in FIG. 7. As shown schematically in FIG. 7, adouble-armed microwave subsystem 700 comprises a magnetron 704 producingmicrowave energy that enters the circulator assembly 703, whichcomprises two circulators, labeled “1” and “2.” Microwave energy passesthrough the circulators substantially as depicted in FIG. 6, to enter apower splitter 706 that directs the microwaves into two waveguide arms709 a and 709 b, within which arms the microwaves are aimed towardstheir respective applicators 710 a and 710 b. In embodiments, thedouble-arm waveguide 709 a and 709 b plus applicators 710 a and 710 bcan split the incident power in a 50:50 ratio, but in other embodiments,a selected ratio of power splitting can be engineered.

Certain maintenance measures within the microwave subsystem can extendthe lifespan of the components and optimize the product output. Inembodiments, for example, the reactor can be cleaned periodically. It isunderstood that carbon soot build-up can occur in the reactor tube whennon-thermal plasma technology is used to convert methane to acetylene,and the presence of soot can lead to localized areas of overheating onthe quartz surface with subsequent damage to the reactor tube. Inaddition, soot that accumulates distal to the microwave coupling canbecome conductive, leading to formation of undesirable arcs. Therefore,in embodiments, regular cleaning of the reactor is undertaken in orderto minimize these problems. Cleaning can be undertaken on a periodicbasis, or based on the discontinuous demands for commercial operation,or in response to observable characteristics of the plasma or effluent.For cleaning purposes, several steps are typically employed: 1)de-energizing the plasma process with in the plasma reaction chamber,either by switching off the microwave power creating the plasma, or byshifting the gas inflow from the process gas to an inert cleaning gas orgas mixture (e.g., pure N₂ or a combination of nitrogen with air or withother cleaning gases), or both; 2) discontinuing the feed gas inflow andintroducing an inert gas mixture (e.g., nitrogen) that purges the inflowlines of the flammable feed gas; 3) filling the reactor with thecleaning gas (e.g., nitrogen mixed with air); 4) re-energizing theplasma reaction chamber with microwave energy to create a plasma statefrom the cleaning gas, including monitoring and adjusting the microwaveenergy and the pressure to permit effective cleaning; 5) reversing theprocess once the reactor tube is clean, with evacuation of the cleaninggas or displacement of the cleaning gas by the feed gas, leading tofilling the reactor tube with the feed gas, and subsequent energizing ofthe feed gas to form a plasma.

In embodiments, soot deposition (and therefore, the need for cleaning)can be minimized by increasing the hydrogen component of the inflowgases; this approach, however, has the drawback of decreased efficiencyin hydrocarbon (e.g., methane) conversion. In other embodiments, sootdeposition can be managed directly by periodic manual cleaning; thisapproach has the drawback of requiring physical interventions to accessthe internal surfaces of the reactor tubing where the soot accumulates.In yet other embodiments, soot deposition can be managed by periodicallychanging the gas inflow into the plasma reaction chamber from thehydrocarbon : hydrogen feedstock used to produce acetylene to a hydrogen: nitrogen mix which, at low power, forms a plasma that removes sootthat has been deposited on the inner surface of the reactor tube. In anembodiment, a pure CO2 plasma can be used as a cleaning plasma. In anembodiment, a hydrogen:nitrogen gas mixture can be used, with a H:Nratio of 5-15:1 can be used, at a power of about 8 kW. In an embodiment,this gas-based cleaning protocol can be carried out on a periodic basis(for example, with a cleaning run of 1-2 minutes every hour or two),aiming for a 1-2% downtime for cleaning out of the continuous runscheme. In other embodiments, a nitrogen: air mixture at a 50:4 ratiocan be used, resulting in a cleaning time of about three minutes every2-3 hours.

An embodiment of this system contains parallel microwave reactor setupsmultiplexed together, with a first reactor and a second reactor joinedafter the reactor tube and heat exchanger and isolation valves for eachreactor but sharing vacuum pumps. A first reactor's magnetron can beshut off and, and the reactor isolated by the isolation valve, thenopened to an alternate vacuum system, while the second reactor isoperating to energize the feedstock gas in its plasma reaction chamber.A cleaning plasma can then be utilized for the first reactor. Once thecleaning is done, the first reactor system will be evacuated of thecleaning gas mixture and purged with nitrogen, then purged again by therespective mixture of new feed gas and recycled gas used for theprocess, then reopened to the main vacuum system and reignited. Thesecond reactor can be cleaned in turn, using the same sequence. In someembodiments, the total number of parallel reactors can be increased toinclude three or more reactors, with their cleaning cycles sequencedsuch that the total throughput of the multiplexed system is constantwhile any one reactor is undergoing cleaning. This cleaning step cantherefore be cycled through the multiplexed reactor system individuallyor in small groups indefinitely, with cycles timed such that there is noloss in product throughput over continuous use.

c. Vacuum Subsystem

In embodiments, a vacuum system is arranged around all componentsbetween the gas injector providing gas inflow to the reactor and theproduct outflow stream distal to the reactor. Maintaining a low pressurein the system contributes to its efficiency (where efficiency ismeasured by eV of energy per mol of methane converted to acetylene). Inembodiments, a vacuum is maintained in the reactor, or a low pressureenvironment is produced, on the order of about 30 to about 120 Torr, orabout 60 to about 100 Torr, or about 70 to about 80 Torr. In anembodiment, an operating pressure of about 70 Torr is maintained for allhydrocarbon feed gases except ethane, which is processed at an operatingpressure of about 120 Torr.

A simplified schematic of a plasma-based hydrocarbon processing system800 highlighting the vacuum subsystem 802 a and 802 b is shown in theFIG. 8, with arrows indicating the direction of gaseous flow throughoutthe system 800. The vacuum subsystem 802 a and 802 b envelopes certaincomponents of the processing system 800 to maintain a pressure in thosecomponents in the range of about 30 to about 120 Torr. As depicted inFIG. 8, the vacuum subsystem designated by the dashed line 802 a createsa first reduced-pressure environment around the reactor 810 and itsoutflow stream 816, and around various components downstream from thereactor 810, all as described in more detail below; the vacuum subsystemdesignated by the dashed line 802 b creates a second reduced pressureenvironment around the gas delivery subsystem 804. For purposes ofclarity, a portion of the vacuum subsystem is identified by dashed line802 a and a portion of the vacuum subsystem is identified by dashed line802 b; these two dashed lines can represent separate subsystems, or theycan be merged together to represent a single vacuum subsystem.Subsystems and components shown in this Figure for clarity include: (i)the gas delivery subsystem 804 that passes the inflow gases, includinghydrocarbon feed gas 806 and hydrogen-containing recycled gas 812,through their respective feed gas inlets (not shown) into the reactor810; (ii) a microwave delivery system 808 a that forms the microwaves808 b that act upon the inflow gases (i.e., the hydrocarbon feed gas 806and the hydrogen-bearing recycled gas 812) in the reactor 810 to effectchemical transformations in the two inflow gases 806 and 812 in theplasma reaction chamber 811 region of the reactor 810, with the productsof these chemical transformations exiting the reactor 810 as the outflowstream 816; (iii) an effluent separation and disposal system comprisingan acetylene separator 814 and a hydrogen separator 818 that separatesthe outflow stream 816 into its gaseous components, with the remainderof the outflow stream 816 distal to the acetylene separator 814 and thehydrogen separator 818 becomes the recycled gas stream 812. As mentionedpreviously and as shown in this Figure, certain components situateddownstream from the reactor 810 are also contained within the vacuumsubsystem as designated by dashed line 802 a, such as a filter 820 forthe outflow stream 816, a heat exchanger/separator 822, and a series ofpumps 824 and 828. In this Figure, a cold trap 830 for removing higherorder hydrocarbons is situated outside the vacuum subsystem asdesignated by dashed line 802 a, as are the acetylene separator 814 andthe hydrogen separator 818.

The filter 820 shown in the Figure is intended to remove carbon solidsfrom the outflow stream 816. In embodiments, the plasma process makes asmall amount of carbon solids as a by-product; for example, carbonsolids can be produced in the range of 0.1-0.5%. Therefore, it isdesirable to filter the outflow stream 816 to remove these carbon solidsin order to prevent these particles from fouling the downstreamcomponents of the system. Since the filter 820 is the first surface thatthe outflow stream 816 encounters after leaving the reactor 810, the gasin this stream is very hot (on the order of 400-1000° C.). Therefore,the material for the filter 820 is selected so that it can withstandsuch temperatures, with or without additional cooling. In embodiments,the filter 820 can be made of ceramic materials or of stainless steel,with cooling added as needed.

d. Cooling subsystem

In embodiments, a cooling subsystem can be implemented to control theoperating temperatures for the various components of the gas processingsystem described herein. In embodiments, the plasma formed in thereactor reaches a temperature between 2000-3000 K (1700-2700° C.),exiting the reactor at a temperature of about 400 to about 1100° C. Toprotect the downstream components of the system from heat damage,cooling is provided. In addition, it is desirable to cool the reactoritself, for example, to keep the outer temperature of the reactor tubebelow 500° C. Moreover, the reactor tube is more likely to retain heatduring gas-based cleaning (as described above) vs during acetyleneproduction, so that more cooling power can be required intermittently toprotect the reactor tube from heat stress. In embodiments, the coolingfor the system includes two types of cooling: water cooling and gascooling. Water cooling can be used for many of the components of thesystem, for example the magnetron, the power supply, the vacuum pumps,the applicator, and the like. Gas cooling can be employed for othercomponents as appropriate, for example, the reactor tube, the reactoritself, and the various O-ring seals in the system.

In embodiments, nitrogen is used for gas cooling. Nitrogen has theadditional benefit of replacing atmospheric gases in enclosed parts ofthe system, thus enhancing safety. In an embodiment, the reactor tubeand the applicator can be enclosed in a sealed, nitrogen-purged(oxygen-free) environment, where the presence of nitrogen providescooling and also serves as a safety mechanism: by replacing the oxygenin the environment around the reactor system, the nitrogen gas coolantreduces the chance of explosion if a leak is created.

e. Effluent Separation and Disposal Subsystem

In embodiments, the outflow stream emerges from the low-pressureenvironment created by the vacuum subsystem, and then undergoes furthermanagement to separate the desired gaseous products from each other andfrom the waste products. Methane and other hydrocarbon-containing gasessuch as ethane, propane, butane and the like produce acetylene andhydrogen when energized in a non-thermal plasma as described herein,along with particulate carbon and higher-order hydrocarbons. To optimizethe economics of the process and to provide a customized gas flow forrecycling, a set of components is positioned distal to the vacuumsubsystem to segregate certain of the gaseous components in the outflowstream from each other.

In embodiments, it is envisioned that a plasma-based hydrocarbonprocessing system and the methods of its use described herein convertmethane in a stoichiometry that is net hydrogen positive, with 1.5 molesof hydrogen being generated for every mole of methane consumed. Theoutflow stream thus contains a mixture of hydrocarbons, including thedesirable product acetylene, along with a predominance of hydrogen. Inembodiments, this hydrogen can be separated from the outflow stream, forexample, by using a membrane separator to separate the hydrogen from theremainder of the effluent. After separation, hydrogen can be purifiedand commercialized as a separate gas product; alternatively, or inaddition, hydrogen can be recycled into the system, as illustrated inprevious Figures. In other embodiments, acetylene can be separated fromthe outflow stream instead of or in addition to hydrogen separation. Forexample, acetylene can be absorbed in an absorption column and thendesorbed and collected. In an embodiment, the outflow stream from thereactor can first be treated to remove particulate carbon andcondensates, and then acetylene can be removed. After the acetylene isremoved, the hydrogen can be optionally removed, captured, or recycled.

As the outflow stream leaves the plasma reaction chamber, it contains acombination of gases, volatilized higher-order hydrocarbons, andparticulate carbon. As previously described, the particulate carbon canbe filtered out immediately downstream from the reactor chamber. Inembodiments, the outflow stream can subsequently be passed through acold trap in order to remove certain higher-order hydrocarbons from theoutflow stream as condensates. After passing through the cold trap, theoutflow stream can be further separated. For example, other higher-orderhydrocarbons can be removed from the outflow stream as described below.These compounds are typically deemed waste products, and they can bediscarded or disposed of after their removal. Following orsimultaneously with the removal of higher-order hydrocarbons, acetyleneand hydrogen are separated from the outflow stream via the effluentseparation and disposal subsystem. The separation process proceeds usingone or more separation technologies, such as adsorption technologies,absorption technologies, chemical reaction technologies such asoxidization or catalyst-mediated conversion, and the like.

i. Adsorption

In certain embodiments, for example, the outflow stream can be passedthrough an adsorption column, where the column contains a highsurface-area adsorbent material that can selectively remove acetylene orhigher-order hydrocarbons from the outflow stream flowing therethrough.In embodiments, adsorbent material can include appropriately sizedmaterials such as activated carbon, zeolites, silica aerogels, molecularsieves, metal-organic frameworks (MOF s), coordination polymers, clays,diatomaceous earth, or pumice. The adsorbent material can be a powder ora film, or it can be formed into spherical pellets, rods, or othershapes which may be useful. These adsorbent materials can be modified bycalcination at elevated temperatures, ion-exchange, or doping withmolecules that increase adsorption affinity or capacity. Additionally, acombination of two or more adsorbent materials can be used to takeadvantage of multiple physical properties. The adsorbent materials canbe contained within a single adsorbent column or divided into multipleadsorbent columns to trap different impurities from the outflow streamin distinct locations. Advantageously, adsorbent materials can beselected to minimize product loss as the outflow stream passes throughthe adsorbent column: in some instances, higher-order hydrocarbonimpurities have a higher affinity for the adsorbent material than doesthe desired product; in other instances, the impurities can displace theproduct molecules off the surface of the adsorbent. In either case,product loss is minimal.

Under certain circumstances, adsorbents can be disposed of after asingle use if the capacity of the adsorbent and the concentration ofimpurities allows for sufficient impurities to be removed beforedisposal. Under other circumstances, for example, if disposal isunfeasible for economic or logistical reasons, the adsorbent can beregenerated and re-used cyclically. Methods for regenerating theadsorbent include pressure reduction, solvent washing, heating, anddisplacement by another gas. During regeneration, the impurities can bedesorbed off the surface of the adsorbent, or they can be convertedin-situ to another chemical that is easier to desorb. If the impuritieshave been converted to an acceptable derivative molecule, this moleculecan be desorbed in-line and released into the process stream. If theimpurities are unaltered on the surface of the adsorbent, so that theycannot be released into the downstream flow, they can be diverted to aside stream to be vented, incinerated or collected for waste disposal.In embodiments, an automated system can arrange for alternation betweenor among multiple adsorber vessels, allowing for regeneration cycles ina continuous operation; such a system has been referred to in the art asa swing adsorber.

Adsorbers can be used for further separation of the outflow stream afterthe removal of higher-order hydrocarbons. Depending on the preferredmode of adsorption and desorption, a pressure swing adsorber (PSA), avacuum swing adsorber (VSA), or a temperature swing adsorber (TSA) canbe used. For example, in certain embodiments, the outflow stream can befed into a PSA system in order to separate hydrogen gas from the outflowstream. In the PSA system, the outflow stream is pressurized and fedinto an adsorption column in which all non-hydrogen components areadsorbed onto the adsorbent material. With all non-hydrogen materialsremoved from the stream a purified hydrogen exits the column. Inembodiments, the feed for the PSA system can be the outflow stream fromthe plasma reactor, or it can be the collected gas from the firstabsorption column described above, or some combination thereof.

Or, for example, the outflow stream can be fed into a TSA system that isadapted for separating higher acetylenes from the outflow stream. Asused herein, the term “higher acetylenes” refers at least to alkynescontaining 3 and 4 carbon atoms, although it can also be applied to allgaseous alkynes and to gaseous aromatics. Through use of a TSA system,higher acetylenes can be separated significantly, even completely, froman acetylene stream without acetylene loss. In embodiments, the higheracetylene molecules can displace acetylene on the surface of anadsorbent, allowing for extreme selectivity in separating the higheracetylenes from the acetylene stream. In order to accomplish this, theadsorption process advantageously is terminated before the higheracetylenes are themselves displaced by an even heavier molecule likebenzene. Therefore, the adsorption cycle in the TSA should be tuned toallow the higher acetylenes to be adsorbed and retained on the adsorbersurface, but to prevent the higher acetylenes from being displaced.Thus, before the higher acetylenes are displaced off the adsorbentsurface, the reactor is closed off to the process stream. The adsorbentcan then be disposed of and replaced, or alternatively, regenerated. Inregeneration, the outflow stream is diverted from the adsorber and hotair (>300° C.) is passed over the adsorbent bed. The impurities arereleased from the adsorbent and either vented or burned. In someiterations, multiple vessels can be used for a continuous operation inwhich some vessels are adsorbing while others are regenerating.

ii. Absorption

In certain embodiments, the outflow stream can be passed through anabsorption column, wherein a solvent at an optimized flow rate runningcounter-current to the outflow stream preferentially absorbshigher-order hydrocarbons from the flowing outflow stream instead ofabsorbing the desired gas product like acetylene. The higher-orderhydrocarbons can then be separated from the solvent in a second column,and the solvent is returned to the absorption column. Examples ofsolvents with stronger affinity for higher-order hydrocarbons over thedesired gas product include methanol, ammonia, toluene, benzene,kerosene, butyrolactone, acetonitrile, propionitrile,methoxypropionitrile, acetone, furfural, N,N-dimethylformamide,N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide,N-formylmorpholine, and N-alkylpyrrolidones, for exampleN-methylpyrrolidone (NMP).

In other embodiments, the outflow stream can be passed through anabsorption column, wherein a solvent having a strong affinity foracetylene and preferably running counter-current to the outflow stream,absorbs acetylene from the flowing outflow stream. The absorbedacetylene can be removed from the solvent by heating the solvent in asecond column for restoring the solvent, and the restored solvent thencan be returned to the absorption column. Examples of solvents withstronger affinity for acetylene over other outflow gases includemethanol, ammonia, toluene, benzene, kerosene, butyrolactone,acetonitrile, propionitrile, methoxypropionitrile, acetone, furfural,N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide,N,N-diethylacetamide, N-formylmorpholine, and N-alkylpyrrolidones, e.g.,N-methylpyrrolidone (NMP).

iii. Chemical Reactions

In certain embodiments, higher-order hydrocarbons in the outflow streamcan be oxidized and thereby removed from the outflow stream. Forexample, certain higher-order hydrocarbons, particularly diacetylene andsubstituted acetylenes such as methylacetylene and vinylacetylene, canbe difficult to separate from acetylene, and they can be removed byconverting them into non-acetylenic compounds. To accomplish this, theoutflow stream can be passed through a column or vessel containing anoxidizing agent, such as a concentrated liquid acid capable of acting asan oxidizing agent, such as nitric acid, sulfuric acid, phosphoric acid,and the like. The higher-order hydrocarbons such as diacetylene and thesubstituted acetylenes can react with the oxidizing agent orconcentrated acid to create other hydrocarbon compounds that can be moreeasily separated from the outflow stream. In certain embodiments, theoutflow stream can be contacted with phosphoric acid on a solid supportto convert the higher-order hydrocarbons such as diacetylene and thesubstituted acetylenes into other hydrocarbon products that can be moreeasily separated from the outflow stream.

In certain embodiments, the outflow stream can be passed through acatalyst bed, using a catalyst that comprises transition metals,transition metal oxides, transition metal salts, or zeolites, in orderto convert various higher-order hydrocarbons into other carbon speciesthat are more readily removable from the gaseous product stream. Whenexposed to a suitable catalyst, these higher-order hydrocarbons can beconverted into a more easily removable compound by catalyst-drivenmechanisms such as polymerization, oxidation, hydrogenation, anddisproportionation. Depending on the mechanistic mode of catalyticconversion and the products obtained, these derivatives of thehigher-order hydrocarbons can be removed through further downstreamprocesses such as are described herein.

iv. Other Separation Technologies

In certain embodiments, higher-order hydrocarbons can be removed fromthe outflow stream by using a condenser, whereby the condenser collectsthese compounds on a high-surface-area material such as silica gel,activated carbon, activated alumina, zeolites, and the like. Forexample, certain higher-order hydrocarbons, e.g., methylacetylene andvinylacetylene, can be difficult to separate from acetylene in gaseousform, but their condensation points (5.01° C. and 10.3° C. respectively)contrast to the condensation point of acetylene (−84° C.) making themsuitable for removal via condensation from the outflow stream. In thisembodiment, a cold bed containing high surface area material attemperatures between −84° C. and 10° C. can effectively condense outhigher-order hydrocarbons from the outflow stream.

In certain embodiments, the outflow stream can be passed through a gasseparation membrane system, wherein gas molecules are separated via sizeexclusion. For example, smaller molecules, such as hydrogen, willpreferentially flow through the membrane element, forming a permeatestream, while larger molecules, such as methane, acetylene, higher-orderhydrocarbons, nitrogen, carbon dioxide, and any other larger molecules,do not flow through the membrane (depending on the porosity of themembrane), forming a retentate stream. In certain embodiments, thepermeate steam is a hydrogen-enriched stream and the retentate stream isa hydrogen depleted stream. Gas separation membrane elements can beformed from a variety of substances, for example: hollow fiber polymermembranes where the polymer can be polycarbonate, polyamide, orcellulose acetate; inorganic membranes where the inorganic material canbe mesoporous silica, zeolite, a metal-organic-framework, or mixed metaloxides; metal membranes where the metal can be palladium orpalladium-silver alloys; and the like. In embodiments, the feed for themembrane separation system can be the outflow stream from the plasmareactor, or it can be the collected gas from the first absorption columndescribed above, or some combination thereof.

Following certain of these outflow separation measures, in embodiments,the outflow stream, containing acetylene, hydrogen, and higher-orderhydrocarbons, can be further separated into its components so that thedesired gaseous products can be retrieved. In other embodiments, theoutflow stream is not subjected to further separation, for example if itis to be used for further chemical processing, or if it is provided to acustomer or end-user as a mixed stream.

f. Data Management and Safety Subsystems

Advantageously, the overall gas production system comprisesinterconnected data management subsystems and safety subsystems, so thatthe safety measures incorporated in these systems and methods areinformed by data collected about the system's performance. Inembodiments, data management can include devices, procedures andalgorithms for data collection and performance diagnosis, and storagefacilities for recording and preserving data. In embodiments,performance diagnosis includes monitoring the state of the system withinnormal parameters to facilitate overall integration and control andidentifying signs of upcoming or active failure states. Opticaldiagnostics can be directed at surveillance of the plasma region, forexample visible light cameras, mid-IR pyrometers, broadbandspectrometers, and the like. Apparatus diagnostics can include pressuretransducers, thermocouples, flow meters, microwave power sensors, andthe like. Other diagnostic equipment can be used as appropriate, forexample full-scale spectrometers and oscilloscopes. In embodiments,various diagnostic modalities can be integrated and monitoredautomatically and/or manually during a run.

In embodiments, the manual and automatic diagnostic procedures can beintegrated with safety procedures, which can include a fault-interlocksystem. In an embodiment, diagnostic input can be actively monitored byhardware and software. If an anomaly is detected, a fault signal can betriggered that activates a predetermined response pattern. For thosemost serious faults, such as a sudden corroborated pressure spike, animmediate automated “hard” shutdown can be triggered. For faults ofmoderate severity, where the consequences are less serious, a slowerautomated shutdown can be triggered, intended to stop operations overthe course of several seconds. For those faults where a parameter isoutside the expected range, but no major consequences are anticipated,the operator can be alerted, so that appropriate actions are taken torectify the situation and clear the fault without requiring a systemshutdown.

3. Exemplary Systems and Subsystems

a. 100 kW-Powered Plasma-Based Hydrocarbon Processing System

A plasma-based hydrocarbon processing system using plasma technology totransform hydrocarbon-containing inflow gas into acetylene and hydrogencan obtain a high degree of source hydrocarbon conversion in combinationwith a high degree of selectivity for the production of acetylene and/orhydrogen. The system described below uses a 100 kW power supply togenerate the microwaves that form the plasma and effect the chemicaltransformations.

The central reaction of this process takes place when methane (derived,for example, from natural gas or biogas) or another C₂-C₄ sourcehydrocarbon is fed into a microwave-energized region, where it breaksdown into a plasma. Without being bound by theory, it is postulated thatthe plasma drives the reaction from the source hydrocarbon to acetyleneand hydrogen by decomposing the hydrocarbon into excited CH_(x) radicalsthat recombine after the plasma energy state to form a spectrum ofhydrocarbon products and hydrogen. Using a C₂-C₄ hydrocarbon as a feedimproves the overall process efficiency as compared to methane, while ahigh degree of selectivity to acetylene can be maintained. However,using methane as contained in natural gas or biogas has the advantage ofoperational efficiency and cost-effectiveness.

The methane conversion process in the 100 kW-powered processing system(i.e., using methane as may be found in a natural gas or biogas feed ora pure methane feed) uses approx. 9.5 kWhr per kg of acetylene productformed, with an acetylene yield of 90%: for the feed gas employed, about90% is converted to acetylene. The resulting product mix is influencedby the non-thermal nature of the plasma temperatures. The gastemperature is 3000-4000 K while the vibrational temperature andelectronic temperatures are two to three times higher, pushing thereaction equilibrium to form acetylene with a high selectivity, and withabundant hydrogen as a byproduct. Hydrogen produced by the plasmareaction can be recycled back into this system as a secondary feed gasthat is used for subsequent reactions, and/or it can be segregated as aseparate gas product. The co-presence of hydrogen and hydrocarbon ascomponents of the reaction reduces the reaction's production of solids.To achieve a desirable proportion of hydrogen and methane for thereaction, the system recycles the produced hydrogen to participate inthe methane-based reactions, as described in more detail below.

i. Overall System

The 100 kW-powered plasma-based hydrocarbon processing system comprisesfour subsystems: gas delivery, microwave, vacuum, and cooling. The gasdelivery subsystem contains two inflow lines. The first inflow line is afeed line conveying a mixed gas such as natural gas continuously sourcedfrom a local utility company or such as upgraded biogas, comprising amixture of predominantly methane, with small amounts of ethane, propane,carbon dioxide, and nitrogen (depending on the source of the raw mixedgas). This inflow may be scrubbed using conventional technologies beforeit enters the plasma reaction chamber, resulting in an almost puremethane stream, with other residual mixed gas components present on theorder of about 100 ppm. The total flow from this inflow line is scalablewith the overall microwave power of the system, with a flow ofapproximately about 3 SLM methane/kW microwave power. A second inflowline conveys recycled gas produced by the reactor that contains about 85to about 90% hydrogen, with small amounts of methane, other reactants,and an amount of unreactive nitrogen of about 5 to about 6%. The totalflow from this inflow line is also scaled with the overall microwavepower of the system, with a flow of about 5 SLM recycled gas/kWmicrowave power.

Each inflow stream is sent into the plasma reaction chamber through itsown inlet that injects its flow into an entry region of a quartz tube toflow through the tube to the region in which the plasma is created. Theinlet for each inflow stream can be angled by a gas injector device toproduce the vortex flow that mixes the streams within the quartz tube asthey flow towards the reaction region, i.e., the plasma reactionchamber. The flow of gas entering through each inlet is controlled bymass flow controllers, adjusted to create a hydrogen-to-methane molarratio of 1.5 H₂:1 CH₄. As the methane is transformed into plasma, aspectrum of reaction products is formed within the plasma reactionchamber within the quartz tube.

When methane is used as a feed gas, about 95% of the methane undergoeschemical change within the plasma. Acetylene accounts for 95% of thehydrocarbons produced from the plasma-energized reactions, giving anoverall approximate 90% acetylene yield. Hydrogen is the other dominantreaction product from these reactions, accounting for approximately 80%of the total outflow stream by volume.

An exemplary 100 kW-powered plasma-based hydrocarbon processing system900 is represented schematically by the block diagram shown in FIG. 9.As shown in this Figure, a central reactor 902, comprising an injectionregion 904, a reaction region 908, and an outflow region 910, receivestwo separate gas streams: (1) a feed gas 912 containing a sourcehydrocarbon (for example the methane in a mixed gas such as natural gasor biogas, or a single C₁-C₄ hydrocarbon, or a customized blend of C₁-C₄hydrocarbons), and (2) a recycled gas flow 914 that includes hydrogenand mixed hydrocarbon-containing gas and optionally unreactive nitrogen.

As schematically represented in the Figure, the inflow gas streams 912and 914 are processed in the reactor 902 to form an outflow stream 918that contains acetylene, hydrogen, and a small proportion of mixedhydrocarbons. The outflow stream 918 is then separated into its gaseouscomponents via a gas separation system 928 (e.g., adsorption,absorption, or a combination thereof, to yield an acetylene stream 920and a hydrogen-dominant gas stream 922 that contains hydrogen 936 and amixture of hydrocarbons 924. Thus diverted from the main outflow stream918 by the gas separation system 928, the acetylene stream 920 can bepurified via further sequestration of impurities in a purificationsystem 926 to yield a purified acetylene gas product 932. Once theacetylene component 920 has been removed from the outflow stream 918,the remaining gas stream 922 is predominantly hydrogen along with amixture of hydrocarbon reaction products, i.e., is hydrogen-dominant.This hydrogen-dominant gas stream 922 can be subjected to furtherseparation if desired, so that hydrogen gas is isolated as a distinctgas stream 930. The hydrogen gas product stream 930 can be furtherpurified as necessary and sold as a product, or it can be recycled backinto the reactor 902 for further reaction with the feed gas 912. In thissystem 900, instead of recycling the hydrogen gas product stream 930,the mixed hydrogen-dominant gas stream 922 is recycled to form therecycled gas flow 914, which is reintroduced into the reactor 902 forfurther reaction with the feed gas 912. Mass flow controllers 940 and942 coordinate the inflow of the feed gas 912 and recycled gas 914 intothe reactor 902 to create the desired ratio of hydrogen to methane (orhydrogen to other source hydrocarbon) in the reactor 902.

ii. Reactor

The reactor identified in FIG. 9 is shown in more detail in FIG. 10.FIG. 10 depicts schematically the reactor 1002, its components, and itsintegration with the microwave subsystem 1004. As depicted, and asoutlined by the grey shadowed box, the microwave subsystem includes apower supply and magnetron complex 1016 for producing the microwaves,and a waveguide assembly 1020 for guiding the microwaves towards areaction region 1012 within the quartz tube where the microwave plasma1018 is formed. As shown in FIG. 10, a quartz tube 1008 contains thecomponents of the reactor 1002: the injection region 1010, the reactionregion or reaction chamber 1012, and the outflow region 1014. Within thequartz tube 1008, the microwave plasma 1018 is generated by themicrowaves (not shown) aimed at the gas flow 1006 within the tube 1008,thereby effecting the transformation of source hydrocarbon into hydrogenand various hydrocarbon-derived products. This quartz tube 1008 isinserted through the broad wall of a microwave waveguide assembly 1020.The size of the quartz tube 1008 depends on the amount of microwavepower used in the system. For the depicted system using 100 kW of powerto produce microwaves, the quartz tube 1008 has an 80 mm outer diameter,a 75 mm inner diameter, a length of 1700 mm, and is maintained at apressure of about 70 Torr by downstream vacuum pumps (not shown). Therelationship of the quartz tube 1008 and the microwave subsystem 1004 isdescribed below in more detail.

As shown in FIG. 10, the recycled gas stream 1022 mixes with the feedgas stream 1024 within the injection region 1010 of the reactor 1002,each stream entering the injection region 1010 of the reactor 1002through its own inlet (not shown). The passage of each gas streamthrough the gas injector device 1032 (also shown schematically in FIG.11) into the reactor 1002 affects its direction, flow rate, andvelocity. As depicted in FIG. 10, an optional gas stream or gas streams1028 can be directed into the injection region 1010, to be blended withthe recycled gas stream 1022 and the feed gas stream 1024 to create avortical gas flow 1006. After mixing, the gases in the gas flow 1006flow distally through the quartz tube 1008, to encounter microwaveenergy produced by the power supply and magnetron complex 1016 anddelivered through the waveguide assembly 1020 into the reaction region1012 of the reactor 1002. The interaction of the microwave energy andthe gas within the reaction region 1012 of the reactor 1002 produces theplasma 1018. The outflow gaseous stream 1034 containing the reactionproducts emerges from the plasma 1018 to enter the outflow region 1038of the quartz tube 1008, to be passed out of the reactor 1002 forfurther separation 1040. As shown in this Figure, a microwave subsystem1004 includes the power supply and magnetron complex 1016 and thewaveguide assembly 1020; not shown in this Figure are additionalelements of the microwave subsystem that are illustrated and describedin the Figures below.

FIG. 11A is a cross-sectional schematic view (not to scale) of anembodiment of a gas injector suitable for use with the 100 kW-poweredplasma-based hydrocarbon processing system, such as the gas injector1032 depicted in FIG. 10. For exemplary purposes, the cross-sectionalview in FIG. 11A corresponds to a cross-section taken at the line A-A′in FIG. 10. FIG. 11A shows a gas injector 1106 situated in a reactionchamber 1102 of a plasma reactor 1100 and providing a plurality of gasflows into the reaction chamber 1102 for those gases to encountermicrowave energy as described above. As shown in this Figure, the gasinjector 1106 provides flow paths for two distinct gas streams into thereactor 1102, with each gas stream directed through its own nozzle andflow path within the gas injector device 1106 and into the reactor 1102.As illustrated in FIG. 11A, there are four injector ports, two for therecycled gas flow 1104 a and 1104 b, and two for the feed gas stream1108 a and 1108 b. In the Figure, the two recycled gas nozzles 1104 aand 1104 b are in fluid communication with a first central flow channel1110 through which the recycled gas stream enters the gas injector 1106and is directed to the recycled gas nozzles 1104 a and 1104 b.Similarly, there is a second centrally-disposed channel 1112 in the gasinjector 1106 for feed gas, where this channel is discrete from thefirst central flow channel 1110 for the recycled gas stream. There aretwo nozzles for feed gas 1108 a and 1108 b, in fluid communication withthe second centrally-disposed channel 1112, with these nozzles 108 a and1108 b entering the reactor 1102 at a different level than the nozzlesfor the recycled gas 1104 a and 1104 b. The nozzles for both types ofgas flow are oriented in directions that are conducive for the formationof a vortex gas flow within the reactor 1102. The channel for recycledgases 1110 and the channel for feed gas 1112 do not intersect with eachother, but rather provide separate gas streams into their respectivenozzles 1104 a/1104 b and 1108a/ 1108 b; neither do the nozzlesintersect with each other, but rather, provide their gas streamsseparately into the reactor 1102. The gas flow through each of thenozzles can be coordinated with the other gas flows in the other nozzlesin terms of flow rate, path length, and pressure drop.

It would be understood by skilled artisans that the relative position ofthe feed gas channel 1112 and the recycled gas channel 1110 can berearranged, for example, as parallel channels, as helices, at differentlevels within the gas injector 1106, or as other arrangements besidesthose shown in FIG. 11A, provided that the channels for each gas arekept separate from each other in the gas injector 1106, and furtherprovided that each distinct gas stream enters the reactor 1102 throughits own discrete nozzle or nozzles. Moreover, the number, configuration,and direction of the nozzles can be varied, provided that the gas streamfor each component gas (i.e., feed gas and recycled gas and any optionaladditional gas) enters the reactor through its own nozzle, withoutcommingling with the other gas stream.

FIG. 11B is a cross-sectional schematic view (not to scale) of anotherembodiment of a gas injector suitable for use with the 100 kW-poweredplasma-based hydrocarbon processing system, such as the gas injector1032 depicted in FIG. 10. For exemplary purposes, the cross-sectionalview in FIG. 11B corresponds to a cross-section taken at the line A-A′in FIG. 10. FIG. 11B shows a gas injector 1156 situated in a reactionchamber 1152 of a plasma reactor 1150 and providing a plurality of gasflows into the reaction chamber 1152 for those gases to encountermicrowave energy as described above. As shown in this Figure, the gasinjector 1156 provides flow paths for two distinct gas streams into thereactor 1152, with each gas stream directed through its own set ofnozzles within the gas injector device 1156 and into the reactor 1152.As illustrated in FIG. 11B, there are eight injector ports or nozzles,four (1154 a, 1154 b, 1154 c, and 1154 d) for a first gas flow, forexample the recycled gas flow, and four (1158 a, 1158 b, 1158 c, and1158 d) for a second gas flow, for example a feed gas stream. In theFigure, the four nozzles for the first gas flow (1154 a, 1154 b, 1154 c,and 1154 d) are in fluid communication with a central flow channel 1162through which the first gas stream enters the gas injector 1156 and isdirected to the appropriate nozzles 1154 a, 1154 b, 1154 c, and 1154 d.The nozzles 1158 a, 1158 b, 1158 c, and 1158 d for the second gas floware each supplied by a separate flow channel 1160 a, 1160 b, 1160 c, and1160 d respectively. Other arrangements of the flow channels to supplythe nozzles 1158 a, 1158 b, 1158 c, and 1158 d for the second gas flowcan be envisioned, provided that the flow channels for the second gasflow do not permit the second gas flow to be commingled with the firstgas flow. Instead, each gas flow is conveyed with its own discrete setof nozzles and its own flow channel(s). The nozzles for the first gasflow 1154 a, 1154 b, 1154 c, and 1154 d, and the nozzles for the secondgas flow 1158 a, 1158 b, 1158 c, and 1158 d, are oriented in directionsthat are conducive for the formation of a vortex gas flow within thereactor 1152. The gas flow through each of the nozzles can becoordinated with the other gas flows in the other nozzles in terms offlow rate, path length, and pressure drop.

iii. Microwave Subsystem

The microwave subsystem shown in FIG. 10 is depicted schematically inFIG. 12, and in more detail. Referring to FIG. 10, a reaction region1012 of the reactor 1002 can be seen intersecting with the waveguideassembly 1020, wherein the microwaves are directed at the gas flow 1006as it enters the reaction region 1012 to form the plasma 1018. Themicrowave subsystem 1004 is responsible for generating the microwavesand directing them towards the reactor 1002.

The microwave subsystem is shown in more detail in FIG. 12. As shown inthis Figure, the microwave subsystem 1200 comprises a power supply 1208,a magnetron 1210, a waveguide assembly 1202 (which includes a waveguide1212 and certain other standard microwave components as describedbelow), and an applicator 1204. The power supply 1208 converts 480V, 150A AC electrical power to 20 kV21 kV, 5.8 A of low-ripple DC power with aconversion of 96% to energize the magnetron 1210. The magnetron 1210,rated at 100 kW, produces continuous microwave power at 83-89%efficiency. The microwaves produced are in the L-band frequency range,approximately 915 MHz. The microwaves are launched into a waveguideassembly 1202, within which a waveguide 1212 directs them through theother components of the system and to the applicator 1204, where theyinteract with the gas/plasma in the plasma reaction chamber 1214. Thewaveguide 1212 features a 90-degree bend 1216. One of the components ofthe waveguide is an isolator 1218 with an attached water load 1220,located distal to the magnetron 1210, to protect the magnetron 1210 fromreflected (un-absorbed) microwaves by directing them with a ferriticcore 1222 to the water load 1220. The other components of the waveguideassembly 1202 allow the microwaves to be guided towards the plasmareaction chamber 1214 and tuned to optimize the creation of the plasmatherein. The applicator 1204 provides the interface between themicrowaves and the quartz tube 1224 within which the plasma is created.Plasma is formed within the plasma reaction chamber 1214, the region ofthe quartz tube 1224 within which the chemical transformations takeplace. As shown in cross-section in FIG. 12, the quartz tube 1224 isdisposed within, but is separated from, the applicator 1204 by an airgap (not labeled).

When the plasma is off and the microwaves are on, a standing wave isformed in the applicator 1204 between the 3-stub tuner 1230 and asliding shorting plate 1232 on the end of the applicator 1204, such thatthe electric field is sufficient to initiate breakdown of the gasmolecules in the quartz tube. Microwave energy entering the applicator1204 is tuned to peak at the center of the plasma reaction chamber 1214,using the shorting plate 1232 as needed to change the length of theplasma reaction chamber 1214 and using the 3-stub tuner 1230 to changethe phase of the incoming microwaves. Once the plasma has beeninitiated, the stub locations in the tuner 1230 can be alteredpreferentially to match the microwave power to the plasma, minimizingun-absorbed power. The 3-stub tuner 1230 contains power and phasesensors (not shown) and can algorithmically adjust the motor-drivenstubs to minimize un-absorbed power. A dual-directional coupler 1234,which contains two small pinholes that couple microwaves with a knownattenuation, is included in the waveguide 1212 proximal to the 3-stubtuner 1230. Power meters (not shown) are connected to these pinholeports and convert the microwave power into a voltage, outputting forwardand reflected power measurements. A thin quartz window 1238 is addedinto the waveguide system to prevent environmental debris and dust fromentering the waveguide components.

b. Torch system for acetylene production

In embodiments, a plasma-based hydrocarbon processing system forproducing acetylene and hydrogen can be of any scale and can deliver arange of purities and acetylene concentrations, depending on the desiredend use. Plasma-based hydrocarbon processing systems as describedpreviously can be designed for small scale applications and can beadapted to the needs of the end user. To facilitate this customization,a plasma-based hydrocarbon processing system can be configured so thatthe outflow (effluent) stream from the reactor is separated into gasstreams having different compositions, for example, a stream having ahigher concentration of acetylene and a stream having a higherconcentration of hydrogen. Small-scale plasma-based hydrocarbonprocessing systems can be designed to deliver pure gas streams, or theycan deliver acetylene-hydrogen mixtures, with or without other gasesincluded in the output gas flow. A small-scale system or “mini-unit” asdescribed above can be designed to produce only acetylene-hydrogenmixtures in its reactor, with gas effluent varying from 0.5%-75%acetylene, therefore minimizing the amount of separation required andreducing the complexity of the system. In embodiments, the end user canmanipulate the parameters of the separation subsystem to produce adesired composition of acetylene admixed with hydrogen; in embodiments,the parameters of the microwave plasma reactor module in the mini-unitcan be adjusted as well, although for more extensive parametercustomization, a larger unit is desirable.

In an embodiment, the overall size of the plasma-based hydrocarbonprocessing system can be scaled, for example from a smaller scale unitsuch as a table-sized mini-unit (e.g., 4 feet wide by 8 feet long by 4feet tall) to a large-scale unit that is 20×20×20 feet or larger. In anembodiment, the plasma-based hydrocarbon processing system can be sizedso that it is portable. Desirable sizing for a portable unit ranges fromthe table-sized dimensions (e.g., 4×8×4) to the size of a standardshipping container. While shipping containers vary in size, a standard20-foot ISO shipping container size would allow transportation of aportable-sized unit; such containers are typically about 8 feet wide, 20feet long, and 8.5 to 9.5 feet high. Other, smaller, shipping containerscan be used for smaller portable devices, for example, those havinglengths of 10 feet or 8 feet, combined with height and width dimensionsas mentioned above.

Such a small-scale system can be attached to small end-user apparatus(e.g., welding torches such as acetylene or oxy-acetylene torches) or tosmall storage facilities or storage tanks. In an embodiment, a 5 kWplasma-based hydrocarbon processing system mini-unit with dimensions of4 feet wide by 8 feet long by 4 feet tall can produce acetylene-hydrogenmixtures of greater than 50% acetylene, in an amount sufficient to feedat least 5 oxy-fuel cutting torches of concurrent, continuous use. Inembodiments, power ranges for a plasma-based hydrocarbon processingsystem mini-unit can range from about 1 kW to about 500 kW, with powerranges selected for desired commercial uses. A plasma-based hydrocarbonprocessing system such as this can be designed to be portable. Asdescribed above, larger units, for example, up to the size of a standardISO 20-foot shipping container, can also be designed to be portable. Inembodiments, a portable plasma-based hydrocarbon processing system canbe deployed to construction sites, demolition sites, shipyards, orremote operations like pipelines or offshore oil rigs, depending on theavailability of a mixed gas stream such as natural gas or biogas,electricity, and water.

FIG. 13 provides a block diagram of a small scale and scalableplasma-based hydrocarbon processing system 1300 suitable for industrialuses. As shown in FIG. 13, a plasma reactor 1302 substantially asdescribed above has an input feed gas 1304 comprising a hydrocarbon suchas methane, ethane, propane, butane, and the like, and derived fromtanks or pipelines such as a natural gas line or a biogas tank or line.This input feed gas 1304 has a preselected inflow calibrated to producean outflow (effluent) gas flow 1306 from the system 1300 ultimatelysuitable for a particular industrial purpose, for example metal cutting.In embodiments, an input feed gas 1304 such as methane or amethane-dense mixture such as natural gas or biogas can be used. Inembodiments, a liquid source of an input feed gas 1304 such as propaneor butane is advantageous, since such feed gas sources may be readilyavailable in certain regions or facilities where a native gas sourcesuch as natural gas or biogas is not available.

In this Figure, the direction of gas flow is indicated by the arrow 1308and other directional arrows. As an example of gas flows useful in thesystem 1300, a gas inflow within the range from about 0 to about 50 SLMcan be selected; in an embodiment, a gas inflow of 5 SLM can produce agas outflow of about 10 SLM. In embodiments, the input feed gas 1304enters the plasma reactor 1302 as a sole gas input. In otherembodiments, a separate gas input from a recycled gas stream 1310 entersthe plasma reactor 1302 through a separate inflow nozzle (not shown), tobe combined with the input feed gas 1304 within the plasma reactor 1302,for example using a gas injector (not shown) as described in previousFigures.

In an embodiment, the outflow 1306 from the plasma reactor 1302 containsabout 14% acetylene, 84% hydrogen, and 2% methane, and it can be furtherprocessed by other components of the system. Entrained in the gaseousoutflow 1306 are various carbon species byproducts, includinghigher-order carbon products and carbon particles, that can be removedprior to delivering a gas product to an end-user in certain embodiments.These byproducts can be removed in solid and liquid traps 1312, throughwhich the outflow gas 1306 passes after being processed in the plasmareactor 1302. After the byproducts are removed, the gas stream 1306 isprocessed through a hydrogen separation membrane system 1314 or apressure swing adsorber that removes hydrogen. Such processing allows anacetylene-rich stream 1318 to be separated from a hydrogen-rich stream1320, with the acetylene-rich stream 1318 being available to theend-user for industrial purposes, e.g., metal cutting. In otherembodiments, there is no advantage to removing the higher-order carbonproducts, for example if the gaseous effluent is to be used for weldingor other industrial uses where a purified acetylene stream isunnecessary. However, it is understood that higher-order carbon productscan foul hydrogen separation membranes, so that these species should beremoved if a hydrogen separation membrane system is used; alternatively,if a mixed effluent stream that includes the higher-order carbonproducts is commercially advantageous, a hydrogen processing system suchas a pressure swing adsorber can be used instead of a hydrogenseparation membrane system.

As shown in the Figure, the acetylene-rich stream 1318, having beenprocessed to remove higher-order carbon products and hydrogen, can bedirected to various end uses or storage 1322. For example, theacetylene-rich stream 1318 can be directed into a pressurized tank, fromwhich end-users can withdraw the gas mixture for use in metal cuttingtorches; advantageously, if the acetylene-rich stream 1318 is stored,the plasma-based hydrocarbon processing system can be run intermittentlyon an as-needed basis to fill the tank(s) for later use. In anembodiment, the acetylene-rich stream 1318 can contain about 50%acetylene, along with other components such as hydrogen, methane, andother gaseous additives as applicable. The acetylene-rich stream 1318can be produced at a flow of about 2.1. SLM. In an embodiment, thehydrogen-rich stream 1320 can contain about 4% acetylene and 96%hydrogen, with a total flow of about 7.9 SLM. In embodiments, two ormore separation membrane systems can be employed to increase theconcentration of acetylene in the acetylene-rich product stream 1318,although a small-scale system can be designed with a single separationmembrane system in order to limit the overall size of the apparatus.

In the plasma-based hydrocarbon processing system embodiment illustratedin FIG. 13, the hydrogen-rich stream 1320 can be directed through asplitter 1322, which can separate the hydrogen-rich stream 1320 into twosubstreams 1320 a and 1320 b, one (1320 a) for end uses, disposal,and/or storage, and one (1320 b) for recycling as a recycled gas stream1310 into the plasma reactor 1302, where it can be processed along withthe input feed gas 1304. The splitter 1322 can be formed from componentsfamiliar to those of skill in the art, such as Y-valves, mass flowcontrollers and the like. The hydrogen-rich substream 1320 a that is notrecycled can be vented, disposed of, collected, burned, or otherwiseused, as required by the specific industrial setting.

The hydrogen-rich sub stream 1320 b used for recycling can have the samecomposition as the sub stream 1320 a that is directed to end uses,disposal, and/or storage. In an embodiment, a recycle flow 1310 of about5 SLM can be redirected into the plasma reactor 1302, having acomposition of about 97.5% hydrogen and 2.5% acetylene, yielding arecycle flow of about 5 SLM hydrogen. With a recycled stream 1310combined with the input feed gas 1304 to fuel chemical transformationsin the plasma reactor 1302, an outflow gas 1306 is produced, asdescribed above. In embodiments, the proportion for recycling can betuned, based on the user's requirements. For recycling, a mass flowcontroller that meters the amount of hydrogen-rich gas 1320 b forrecycling offers particular consistency, with the remainder directed toend-uses, disposal, or storage.

FIG. 14 shows, in more detail, a modular plasma-based hydrocarbonprocessing system 1400 suitable for small-scale or larger-scale use,with arrows showing directions for gas flow. As shown in FIG. 14, a gaspipeline 1404, for example, a natural gas pipeline, can provide theinflow gas for the microwave plasma reactor 1402, although any source ofinflow gas can be used (a supply tank containing the gas, for example,as would be available for C₁-C₄ alkanes, or a line or tank deliveringbiogas). The inflow gas can be supplemented by a recycled stream 1408containing a hydrogen-rich gas. Following processing in the microwaveplasma reactor 1402, the outflow (effluent) gas passes through a heavyliquids trap 1412 that removes the higher-order hydrocarbons using acombination of a cold trap and/or a carbon adsorber. As a next stage,the outflow gas passes through a filter 1414 that removes particulatematter, for example carbon soot. The gas pressure is then adjusted by avacuum pump 1418 and then the gas is compressed by a compressor 1422 topass through a hydrogen separator 1424. The plasma reactor 1402, theheavy liquids trap 1412, the solids filter 1414, and the vacuum pump1418 are grouped together as the reactor subsystem 1420. This may belocated in proximity to the hydrogen recycle subsystem 1410 and theeffluent management subsystem 1434, or these subsystems can be in fluidcommunication with each other but arranged remotely from each other, asis convenient for a particular industrial application.

As mentioned previously, the hydrogen separator 1424 can include one ormore hydrogen separation units; in an exemplary embodiment, eachhydrogen separation unit can contain one or more hydrogen separationmembranes, but other configurations and separator technologies (forexample, pressure swing adsorber technology to separate hydrogen) can beemployed. The configurations of the hydrogen separator units areadaptable to permit lesser or greater acetylene enrichment in theeffluent acetylene-rich stream 1428. Depending on the desired industrialuse, this effluent stream 1428 can be used directly as a cutting stream,or it can be stored as a product stream. In an embodiment, the gasremaining after the acetylene-rich stream 1424 is removed contains alarge proportion of hydrogen. As previously described, thishydrogen-rich stream can be split into two sub streams in a splitter1432, with one stream 1408 designated for recycle, and one stream 1430for disposal, venting, burning, commercialization, or other uses asdesired.

Effluent management subsystems, substantially as described previously,can be integrated with the reactor subsystem (including a gas deliverysubsystem, a microwave subsystem, and a vacuum subsystem, previouslydescribed but not shown in FIG. 14) within a single mini-unit forspecific applications. The size, number, and complexity of thecomponents required for the effluent separation processes can affect thesize of the system overall. In an embodiment, a single plasma reactorcan utilize a single hydrogen separation subsystem to provide a smallfootprint, with the subsystem including one or two hydrogen-separatingmembranes or other separation subsystem technologies, such as pressureswing adsorption. In an embodiment, separation subsystems, for examplefor hydrogen separation, can be integrated with the plasma-basedhydrocarbon processing system.

In an embodiment of a modular plasma-based hydrocarbon processing systemusing a single hydrogen separation unit with a single separationmembrane, the outflow gas from the reactor can contain the followinggaseous components, at a flow rate of 10 SLM: 14% acetylene, 81%hydrogen, 2% methane, and 3% nitrogen. Following processing through ahydrogen separation unit having a single separation membrane, ahydrogen-rich stream is formed, containing the following gaseouscomponents at a flow rate of 7 SLM: 4% acetylene, 96% hydrogen.Simultaneously, an acetylene-rich stream is formed, containing thefollowing gaseous components at a flow rate of 3 SLM: 50% acetylene, 27%hydrogen, 9% methane, and 14% nitrogen. Using this process, 93.75%acetylene retention is accomplished in the acetylene-rich stream, and86.5% of hydrogen is recycled. The flow rates and mol ratios of thecomponents of the various gas streams for the one-membrane hydrogenseparation system are shown in Table 3 below:

TABLE 3 Plasma Reactor Acetylene-rich Hydrogen-rich Effluent streamstream Vent/burn Recycle Stream Flow Rate mol Flow Rate mol Flow Ratemol Flow Rate mol Flow Rate mol (SLM) ratio (SLM) ratio (SLM) ratio(SLM) ratio (SLM) ratio H₂ 8.1 0.81 0.567 0.268 7.53 0.956 3.53 0.956 40.956 CH₄ 0.2 0.02 0.2 0.094 0 0 0 0 0 0 N₂ 0.3 0.03 0.3 0.142 0 0 0 0 00 C₂H₂ 1.4 0.14 1.05 0.496 0.35 0.044 0.164 0.044 0.186 0.044 Total 102.12 7.88 3.694 4.186

A double-membrane hydrogen separation unit can extract more hydrogenfrom the reactor's outflow gas, yielding a hydrogen-rich streamcontaining 1.2% acetylene and 98.8% hydrogen, at a flow of 7 SLM. Withthis system, an acetylene-rich stream is formed containing the followinggaseous components at a flow rate of 3 SLM: 45% acetylene, 38% hydrogen,7% methane, and 10% nitrogen. The flow rates and mol ratios of thecomponents of the various gas streams for the two-membrane hydrogenseparation system are shown in Table 4 below:

TABLE 4 Plasma Reactor Acetylene-rich Hydrogen-rich Effluent streamstream Vent/burn Recycle Stream Flow Rate mol Flow Rate mol Flow Ratemol FlowRate mol FlowRate mol (SLM) ratio (SLM) ratio (SLM) ratio (SLM)ratio (SLM) ratio H2 8.1 0.81 1.09 0.376 7.006 0.988 3.53 0.988 4 0.988CH4 0.2 0.02 0.2 0.069 0 0 0 0 0 0 N2 0.3 0.03 0.3 0.103 0 0 0 0 0 0C2H2 1.4 0.14 1.05 0.452 0.088 0.012 0.038 0.012 0.05 0.012 Total 102.12 7.094 3.568 4.05

A wide variety of industrial uses can be envisioned for small scale ormodular plasma-based hydrocarbon processing systems as described herein.As mentioned above, a major industrial use for acetylene is in themetalworking industry, for example, in metal cutting. For thesepurposes, an appropriately sized plasma-based hydrocarbon processingsystem in accordance with this disclosure can be used directly or viastorage tanks to provide fuel for metal cutting. In addition, theplasma-based hydrocarbon processing system can be coupled with othersystems to provide product versatility and to increase efficiency in themetalworking industry. As an example, in oxy-acetylene steel cuttingfacilities, the plasma-based hydrocarbon processing system can be usedin conjunction with air separation units (ASUs). The ASU can separateair into nitrogen-rich and oxygen-rich streams, which can then becombined with the gas stream(s) used by or produced by microwave plasmareactor unit. Using this combination of apparatus, an operator cangenerate all the gas feedstock required for steel fabrication on-site.

EXAMPLES Example 1

A flow of precursor gas, comprised of 60 standard liters per minute of99.9% purity methane, 90 standard liters per minute of 99.9% purityhydrogen, and 6 standard liters per minute of nitrogen, was suppliedthrough a gas injector apparatus similar to that described in FIGS. 4Aand 4B, into an 50 mm outer diameter, 45 mm inner diameter quartz tubekept at a pressure of 70 Torr. The precursor gas was subjected to 19 kWof incident 915 MHz microwave power in a plasma reactor apparatussimilar to that described in FIG. 3. 95.7% of the methane contained inthe precursor gas was converted to hydrogen and hydrocarbon products.The hydrocarbon composition of the outflow gas leaving the reactor isdescribed in Table 5 below, as analyzed by a gas chromatograph.

TABLE 5 Component Mol % Acetylene 15.12 Hydrogen 82.97 Methane 1.41Ethylene 0.14 Propane 0.01 Propadiene 0.01 Diacetylene 0.29 VinylAcetylene 0.03 Benzene 0.02 Carbon Solids and higher-order hydrocarbonsTrace

The outflow gas from the reactor was passed through an air-cooled heatsink and then passed through corrugated-paper filters before exiting thevacuum pump. The outflow gas then passed through a cold trap operatingat 10° C. and additional filter.

A portion of outflow gas was then passed through an adsorption columncontaining high surface area activated carbon. Outflow gas compositionat the adsorption column exit is shown in Table 6 below.

TABLE 6 Mol Percent before Mol Percent after Component AdsorptionAdsorption Acetylene 15.12 15.17 Hydrogen 82.97 83.25 Methane 1.41 1.41Ethylene 0.14 0.14 Propane 0.01 0.1 Propadiene 0.01 0.1 Diacetylene 0.290 Vinyl Acetylene 0.03 0 Benzene 0.02 0 Carbon Solids Trace 0 HigherOrder Trace 0 Hydrocarbons

After leaving the adsorption column, a portion of the outflow gas wasthen passed through an absorption column. A solvent, N-Methylpyrrolidone, was flowed counter-currently to the outflow gas topreferentially absorb acetylene. Exiting the absorption column, thesolvent with the absorbed acetylene was pumped into a second column forrestoring the solvent and heated to 120-140° C. In the second column,the acetylene and associated gases were removed from the solvent as apurified product gas stream and the restored solvent was recycled intothe system. Table 7 below shows the composition of the purified productgas stream emanating from the second column.

TABLE 7 Component Mol Percent Acetylene 98.764 Hydrogen 0.774 Methane0.211 Ethylene 0.083 Ethane 0.002 Propylene 0.042 Diacetylene 0.002Vinyl Acetylene 0.006 Carbon Dioxide 0.115 Toluene 0.001

Example 2

A flow of precursor gas, comprised of 20 standard liters per minute of99.9% purity methane, 20 standard liters per minute of ethane, 95standard liters per minute of 99.9% purity hydrogen, and 6 standardliters per minute of nitrogen was supplied through a plasma reactorapparatus as described in Example 1 and reacted with 18 kW of incident915 MHz microwave power using the plasma reactor apparatus used inExample 1. 97.9% of the methane and ethane contained feed gas wasconverted to hydrogen and hydrocarbon products. The hydrocarboncomposition of the outflow gas from the reactor is described in Table 8below, as analyzed by a gas chromatograph.

TABLE 8 Component Mol % Acetylene 16.70 Hydrogen 72.73 Methane 0.75Ethylene 0.35 Propane 0.01 Propadiene 0.01 Diacetylene 0.38 VinylAcetylene 0.05 Benzene 0.03 Carbon Solids Trace Higher-Order HCs

Example 3

A flow of precursor gas, comprised of 110 standard liters per minute of99.9% purity methane and 11 standard liters per minute of nitrogen, wassupplied through a gas injector apparatus, similar to that described inFIGS. 4A and 4B, into an 80 mm outer diameter, 75 mm inner diameterquartz tube. The precursor gas was subjected to 11 kW of incident 915MHz microwave power in a plasma reactor apparatus as described in FIG.3. 50.7% of the methane contained in the precursor gas was converted tohydrogen and hydrocarbon products. 7% of the converted methane yieldedcarbon solids and polycyclic aromatic hydrocarbons. 76% of the convertedmethane yielded acetylene.

Example 4

A flow of precursor gas, comprised of 100 standard liters per minute of99.9% purity methane, 160 standard liters per minute of 99.9% purityhydrogen, and 10 standard liters per minute of nitrogen, was suppliedthrough a gas injector apparatus similar to that described in FIGS. 4Aand 4B, into an 50 mm outer diameter, 45 mm inner diameter quartz tubekept at 70 Torr. The precursor gas was subjected to 29 kW of incident915 MHz microwave power in a plasma reactor apparatus similar to thatdescribed in FIG. 3. 90.3% of the methane contained in the precursor gaswas converted to hydrogen and hydrocarbon products. The hydrocarboncomposition of the outflow gas leaving the reactor is described in Table9 below.

TABLE 9 Component Mol % Hydrogen 83.42729 Methane 2.99563 Propane0.010008 Propylene 0.010008 Propadiene 0.060046 Methyl Acetylene0.010008 1,3-butadiene 0 Vinyl Acetylene 0.020015 Diacetylene 0.253528Ethylene 0.143443 Ethane 0 Acetylene 13.05334 Benzene 0.016679 Toluene 0

Example 5

A flow of precursor gas, comprised of 130 standard liters per minute of99.9% purity methane, and 13 standard liters per minute of nitrogen, wassupplied through a gas injector apparatus similar to that described inFIGS. 4A and 4B, into an 80 mm outer diameter, 75 mm inner diameterquartz tube kept at 48 Torr. The precursor gas was subjected to 24.3 kWof incident 915 MHz microwave power in a plasma reactor apparatussimilar to that described in FIG. 3. 85.2% of the methane contained inthe precursor gas was converted to hydrogen and hydrocarbon products.

Example 6

A flow of precursor gas, comprised of 74 standard liters per minute of99.9% purity methane, 40 standard liters per minute of 99.9% purityhydrogen, and 88 standard liters per minute of nitrogen, was suppliedthrough a gas injector apparatus similar to that described in FIGS. 4Aand 4B, into an 80 mm outer diameter, 75 mm inner diameter quartz tubekept at 70 Torr. The precursor gas was subjected to 23.9 kW of incident915 MHz microwave power in a plasma reactor apparatus similar to thatdescribed in FIG. 3. 95.1% of the methane contained in the precursor gaswas converted to hydrogen and hydrocarbon products.

Example 7

A flow of precursor gas, comprised of 47 standard liters per minute of99.9% purity methane, 110 standard liters per minute of 99.9% purityhydrogen, and 5 standard liters per minute of nitrogen, was suppliedthrough a gas injector apparatus similar to that described in FIGS. 4Aand 4B, into an 80 mm outer diameter, 75 mm inner diameter quartz tubekept at 65 Torr. The precursor gas was subjected to 15.6 kW of incident915 MHz microwave power in a plasma reactor apparatus similar to thatdescribed in FIG. 3. 89.7% of the methane contained in the precursor gaswas converted to hydrogen and hydrocarbon products.

Example 8

A flow of precursor gas, comprised of 90 standard liters per minute of99.9% purity methane, 135 standard liters per minute of 99.9% purityhydrogen, and 9 standard liters per minute of nitrogen, was suppliedthrough a gas injector apparatus similar to that described in FIGS. 4Aand 4B, into an 38 mm outer diameter, 35 mm inner diameter quartz tubekept at 105 Torr. The precursor gas was subjected to 25 kW of incident915 MHz microwave power in a plasma reactor apparatus similar to thatdescribed in FIG. 3. 92.0% of the methane contained in the precursor gaswas converted to hydrogen and hydrocarbon products.

Example 9

A flow of precursor gas, comprised of 15 standard liters per minute of99.9% purity butane, 90 standard liters per minute of 99.9% purityhydrogen, and 6 standard liters per minute of nitrogen, was suppliedthrough a gas injector apparatus similar to that described in FIGS. 4Aand 4B, into an 50 mm outer diameter, 45 mm inner diameter quartz tubekept at 50 Torr. The precursor gas was subjected to 17.7 kW of incident915 MHz microwave power in a plasma reactor apparatus similar to thatdescribed in FIG. 3. 100% of the butane contained in the precursor gaswas converted to hydrogen and hydrocarbon products with a 0.6% methaneyield.

Example 10

A flow of precursor gas, comprised of 30 standard liters per minute of99.9% purity ethane, 90 standard liters per minute of 99.9% purityhydrogen, and 6 standard liters per minute of nitrogen, was suppliedthrough a gas injector apparatus similar to that described in FIGS. 4aand 4b , into an 50 mm outer diameter, 45 mm inner diameter quartz tubekept at 126 Torr. The precursor gas was subjected to 16 kW of incident915 MHz microwave power in a plasma reactor apparatus similar to thatdescribed in FIG. 3. 100% of the ethane contained in the precursor gaswas converted to hydrogen and hydrocarbon products with 3.3% methaneyield. The hydrocarbon composition of the outflow gas leaving thereactor is described in Table 10 below.

TABLE 10 Component Mol % acetylene 18.34358 hydrogen 79.93364 methane0.824195 ethane 0.003651 ethylene 0.383346 propane 0.006845 propadiene0.008215 propylene 0 diacetylene 0.412097 vinyl acetylene 0.054307methyl acetylene 0 benzene 0.028751 toluene 0.001369

Example 11

A flow of precursor gas, comprised of 8.6 standard liters per minute of99.9% purity propane, 8.6 standard liters per minute of 99.9% puritybutane, 88 standard liters per minute of 99.9% purity hydrogen, and 6standard liters per minute of nitrogen, was supplied through a gasinjector apparatus similar to that described in FIGS. 4A and 4B, into an50 mm outer diameter, 45 mm inner diameter quartz tube kept at 70 Torr.The precursor gas was subjected to 16 kW of incident 915 MHz microwavepower in a plasma reactor apparatus similar to that described in FIG. 3.100% of the ethane contained in the precursor gas was converted tohydrogen and hydrocarbon products with a 3.2% methane yield. Thehydrocarbon composition of the outflow gas leaving the reactor isdescribed in Table 11 below.

TABLE 11 Component Mol % acetylene 20.33077 hydrogen 77.56967 methane1.155769 ethane 0 ethylene 0.293664 propane 0.008498 propadiene 0.013692propylene 0 diacetylene 0.549557 vinyl acetylene 0.046269 methylacetylene 0 benzene 0.030688 toluene 0.001416

Example 12

A plasma reactor system as described in Example 1 that produces 250liters of outflow gas per minute was used. After the vacuum pump in thesystem, solid carbon byproducts were removed with a simple in-linefilter. Liquid hydrocarbon condensates containing greater than 14 carbonatoms were separated from the stream in a cold trap operating at -20° C.No further hydrocarbons were removed, and the outflow was directlypassed through a stainless-steel vessel with an internal diameter of 8inches containing 0.4 kg of blank 100-200 mesh a-alumina mixed with 1.8kg of 100-200 mesh a-alumina doped with 3wt % metallic palladium and 4wt% metallic silver. The catalyst bed was maintained at 350° C. withinternal, open-loop water cooling system. A gas mixture was obtainedthat contains 50% hydrogen, 11% ethylene, 0.5% ethane and 38.5% methane;acetylene content in the gas mixture was deliberately kept below 100ppm.

Example 13

A plasma reactor system as described in Example 1 was used. A stream of1 liter of outflow gas per minute was split off and processed further asdescribed in this example. After the vacuum pump, solid carbonbyproducts were removed with a ceramic, regenerative filter. Liquidhydrocarbon condensates containing greater than 10 carbon atoms wereseparated from the stream in a cold trap operating at −30° C.Afterwards, the outflow gas was passed through a stainless-steel vesselcontaining 20 grams high-surface area activated carbon, doped with 0.01%metallic palladium. The outflow gas at this point contained 85%hydrogen, 8% acetylene, 4% ethylene, and 0.6% vinyl acetylene andbalance methane. The vinyl acetylene was removed by bubbling through a500 mL vessel containing 300 mL of concentrated sulfuric acid at roomtemperature, then through a vessel containing 100 mL room temperaturewater to trap the volatized sulfuric acid. Finally, the gas stream wasdried by passing through 10 grams of calcium sulfate desiccant.

While this invention has been particularly shown and described withreferences to preferred embodiments thereof, it will be understood bythose skilled in the art that various changes in form and details may bemade therein without departing from the scope of the inventionencompassed by the appended claims. Unless otherwise indicated, allnumbers expressing reaction conditions, quantities, amounts, ranges andso forth, as used in this specification and the claims are to beunderstood as being modified in all instances by the term “about.”Accordingly, unless indicated to the contrary, the numerical parametersset forth herein are approximations that can vary depending upon thedesired properties sought to be obtained by the present invention.

What is claimed is:
 1. A method for processing a methane-containinginflow gas to produce outflow gas products, comprising directing themethane-containing inflow gas into a system comprising: a gas deliverysubsystem, a plasma reaction chamber, a microwave subsystem, a vacuumsubsystem, and an effluent separation and disposal subsystem; i. whereinthe gas delivery subsystem is in fluid communication with the plasmareaction chamber and directs the methane-containing inflow gas into theplasma reaction chamber, the gas delivery subsystem comprising adelivery conduit and a gas injector, wherein the gas injector comprisesan injector body comprising two or more separate gas feeds, a first gasfeed conveying the methane-containing inflow gas into the plasmareaction chamber through a first set of one or more nozzles, and asecond gas feed conveying a hydrogen-rich reactant gas into the plasmareaction chamber through a second set of one or more nozzles, whereinthe delivery conduit is in fluid communication with the gas injector,wherein the delivery conduit comprises a feed gas conveying circuit thatdelivers the methane-containing inflow gas into the gas injector, andwherein the delivery conduit further comprises an auxiliary gasconveying circuit that delivers the hydrogen-rich reactant gas into thegas injector, each of the methane-containing inflow gas and thehydrogen-rich reactant gas being delivered into the gas injector,through the gas injector, and into the plasma reaction chamber through aseparate pathway; ii. wherein the plasma reaction chamber is disposedwithin an elongate reactor tube, the elongate reactor tube having aproximal end and a distal end and being dimensionally adapted forinteraction with the microwave subsystem, iii. wherein the microwavesubsystem comprises an applicator that interacts with the elongatereactor tube by directing the microwave energy into the plasma reactionchamber, wherein the plasma reaction chamber is disposed in a region ofthe elongate reactor tube that passes through the applicator andintersects it perpendicularly, wherein the microwave subsystem producesmicrowave energy and directs the microwave energy into the plasmareaction chamber to energize the methane-containing inflow gas and thehydrogen-rich reactant gas within the region of the elongate reactortube to form a non-thermal plasma, and wherein the non-thermal plasmatransforms the methane in the methane-containing inflow gas and thehydrogen in the hydrogen-rich reactant gas into the outflow gasproducts, wherein the outflow gas products comprise acetylene andhydrogen; wherein the outflow gas products flow within the plasmareaction chamber towards the distal end of the elongate reactor tube andemerge from the distal end to form an effluent stream that enters aneffluent separation and disposal subsystem in fluid communication withthe elongate reactor tube, and iv. wherein the effluent separation anddisposal subsystem comprises at least one of a hydrogen separationsubsystem for removing the hydrogen from the effluent stream, anacetylene separation subsystem for removing the acetylene from theeffluent stream, and a temperature swing adsorber for removing higheracetylenes from the effluent stream.
 2. The method of claim 1, whereinthe hydrogen-rich reactant gas comprises a recycled gas formed from aportion of the outflow gas products and wherein the recycled gas isdelivered through a recycled gas conveying circuit into the auxiliarygas conveying circuit to form at least a portion of the hydrogen-richreactant gas that enters into the gas injector.
 3. The method of claim2, wherein the hydrogen-rich reactant gas consists essentially ofhydrogen.
 4. The method of claim 1, wherein the two or more separate gasfeeds are coaxially arranged.
 5. The method of claim 1, wherein theelongate reactor tube comprises a proximal portion at the proximal end,wherein the gas injector conveys the methane-containing inflow gas, andthe hydrogen-rich reactant gas into a proximal portion, and themethane-containing inflow gas and the hydrogen-rich reactant gas flowdistally therefrom towards the plasma reaction chamber.
 6. The method ofclaim 1, wherein at least one of the one or more nozzles in the firstset of one or more nozzles or the second set of one or more nozzles isoriented at an angle to a longitudinal axis of the plasma reactionchamber or at an angle to a transverse axis of the plasma reactionchamber.
 7. The method of claim 1, wherein at least one of the one ormore nozzles in the first set of one or more nozzles or the second setof one or more nozzles is oriented at an angle to a longitudinal axis ora transverse axis of the injector body.
 8. The method of claim 1,wherein the methane-containing inflow gas entering the plasma reactionchamber from the first set of one or more nozzles and the hydrogen-richreactant gas entering the plasma reaction chamber from the second set ofone or more nozzles create a vortex of the gases within the plasmareaction chamber.
 9. The method of claim 1, wherein the hydrogenseparation subsystem is downstream from the acetylene separationsubsystem and in fluid communication therewith.
 10. The method of claim1, wherein the hydrogen separation subsystem is in fluid communicationwith a recycled gas conveying circuit, wherein at least a portion ofhydrogen removed from the effluent stream by the hydrogen separationsubsystem is recycled into the recycled gas conveying circuit into theauxiliary gas conveying circuit to form at least a portion of thehydrogen-rich reactant gas that enters into the gas injector.
 11. Themethod of claim 1, wherein the acetylene separation subsystem and thehydrogen separation subsystem are downstream from the temperature swingadsorber.
 12. The method of claim 11, wherein the hydrogen separationsubsystem is downstream from the acetylene separation subsystem.
 13. Themethod of claim 1, wherein the effluent separation and disposalsubsystem comprises at least two of the following: a hydrogen separationsubsystem for removing hydrogen from the effluent stream, an acetyleneseparation subsystem for removing acetylene from the effluent stream,and a temperature swing adsorber for removing higher acetylenes from theeffluent stream.
 14. The method of claim 13, wherein the effluentseparation and disposal subsystem comprises the hydrogen separationsubsystem for removing hydrogen from the effluent stream, the acetyleneseparation subsystem for removing acetylene from the effluent stream,and the temperature swing adsorber for removing higher acetylenes fromthe effluent stream.
 15. The method of claim 1, wherein the effluentseparation and disposal subsystem further comprises a filter for removalof carbon solids upstream of the acetylene separation subsystem.
 16. Themethod of claim 15, wherein the effluent separation and disposalsubsystem further comprises a cold trap for removing higher orderhydrocarbons as condensates.
 17. The method of claim 16, wherein theacetylene separation subsystem and the hydrogen separation subsystem aredownstream from the temperature swing adsorber.
 18. The method of claim17, wherein the hydrogen separation subsystem is downstream from theacetylene separation subsystem.
 19. The method of claim 1, wherein thevacuum subsystem maintains a reduced pressure environment within theelongate reactor tube.
 20. The method of claim 19, wherein the vacuumsubsystem maintains a reduced pressure environment for the outflow gasproducts.
 21. The method of claim 19, wherein the vacuum subsystemmaintains a reduced pressure environment for the gas delivery subsystem.22. The method of claim 1, wherein the gas delivery subsystem conveysthe methane-containing inflow gas and the hydrogen-rich reactant gasinto the plasma reaction chamber such that the ratio of the methane tothe hydrogen is about 1:1-3.
 23. The method of claim 22, wherein theratio is about 1:1-2.
 24. The method of claim 22, wherein the ratio isabout 1:1.5.